CN101784893B - Integral adsorption piece and sample adsorption method and device using same - Google Patents

Integral adsorption piece and sample adsorption method and device using same Download PDF

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CN101784893B
CN101784893B CN200880103664.3A CN200880103664A CN101784893B CN 101784893 B CN101784893 B CN 101784893B CN 200880103664 A CN200880103664 A CN 200880103664A CN 101784893 B CN101784893 B CN 101784893B
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adsorbent
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integral
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CN101784893A (en
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佐藤睦
寺岛弘之
武井义之
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GL Sciences Inc
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Abstract

The present invention addresses the problem of obtaining a monolith adsorbent capable of simply trapping a target sample in a short time or even in a small amount or an excessive amount of sample, extracting the sample with a small amount of solvent, and easily securing a sample necessary for analysis, and an adsorption/holding method and device using the monolith adsorbent. The solution is that the monolithic adsorption piece of the invention is composed of: the surface of the monolithic structure is treated with a hydrophobic or hydrophilic compound or resin by allowing the monolithic structure to contain an adsorbent such as activated carbon or graphite and exposing the adsorbent to the surface of the structure.

Description

整体吸附件及利用其的试样吸附方法及装置Integral adsorption piece and sample adsorption method and device using same

技术领域 technical field

本发明涉及整体吸附件及利用所述整体吸附件的试样吸附方法及装置。The invention relates to an integral adsorbent and a sample adsorption method and device using the integral adsorbent.

背景技术 Background technique

作为向分析装置(GC，LC等)导入试样用的试样萃取方法，提案有固相微萃取(solid phase microExtraction，SPME)法和搅拌棒吸附萃取(stir bar sorption extraction，SBSE)法等。As a sample extraction method for introducing a sample into an analysis device (GC, LC, etc.), a solid phase microextraction (SPME) method, a stir bar adsorption extraction (SBSE) method, etc. have been proposed.

两者是应用将固定相设定为液相的溶剂萃取的原理的试样萃取方法，利用根据分配系数进行的物质移动。因而，在迅速进行高回收率的试样萃取的情况下，存在固定相的种类·膜厚、萃取温度、盐析、萃取时间、试样量、pH调整、夹杂成分的影响、搅拌速度等各种各样的因素，使用起来有难度。Both are sample extraction methods using the principle of solvent extraction in which the stationary phase is set as a liquid phase, and utilize material movement based on a partition coefficient. Therefore, in the case of rapid extraction of a sample with a high recovery rate, there are various factors such as the type of stationary phase, film thickness, extraction temperature, salting out, extraction time, sample amount, pH adjustment, influence of inclusion components, and stirring speed. Various factors make it difficult to use.

如日本特许第3081239号所公开的那样，SPME是为了通过相平衡保持溶液中的溶质成分和通过玻璃纤维、玻璃等包覆的PDMS等液相、或混合在液相中的吸附件保持溶质成分的浓缩方法。As disclosed in Japanese Patent No. 3081239, SPME is to maintain the solute component in the solution through phase equilibrium and maintain the solute component through a liquid phase such as PDMS coated with glass fiber, glass, etc., or an adsorbent mixed in the liquid phase method of concentration.

将用这种方法保持的溶质成分直接插入到GC注入口内部，能够使其在GC注入口内部气化、解吸。The solute components held in this way can be directly inserted into the GC inlet, and can be vaporized and desorbed inside the GC inlet.

另外，如日本特许第3462443号所公开的那样，SBSE还具有以下功能：将PDMS等液相涂布在内置磁石的玻璃片的周围，放入容器中，可以在目标试样中搅拌。In addition, as disclosed in Japanese Patent No. 3462443, SBSE also has the function of coating a liquid phase such as PDMS around a glass plate with a built-in magnet, putting it in a container, and stirring it in a target sample.

作为能够非常廉价、简单地实现浓缩分析的方法，上述方法正在以食品、香气成分净水VOC、空气、农药等的简便的浓缩分析器具的形式普及。As a method capable of very cheap and simple concentration analysis, the above-mentioned method is spreading in the form of a simple concentration analysis device for food, aroma components, purified water VOC, air, pesticides, and the like.

利用相平衡实施的现行的SPME的溶液的试样的保持率通常为百分之几至30％左右。在SPME或SBSE中，为了更好地萃取试样溶液中的物质(提高分配系数)而增加固定相体积，因此，需要增加试样捕集量。The retention rate of a sample of a conventional SPME solution performed by phase equilibrium is usually several percent to about 30%. In SPME or SBSE, in order to better extract substances in the sample solution (increase the partition coefficient), the volume of the stationary phase is increased, therefore, the amount of sample capture needs to be increased.

但是，固定相体积的增加与其厚度相关联，其结果，为了使固定相中的浓度和试样溶液中的浓度达到平衡状态就要花费时间。However, the increase in the volume of the stationary phase is related to its thickness, and as a result, it takes time for the concentration in the stationary phase and the concentration in the sample solution to reach an equilibrium state.

另外，为了用热或溶剂从试样溶液中萃取(脱附)吸附的目标物质也要花费时间，色谱的峰就会变宽。In addition, it takes time to extract (desorb) the adsorbed target substance from the sample solution with heat or a solvent, and the peak of the chromatogram becomes broad.

进而，由于长时间消耗热量，还存在目标成分发生分解这样的缺点。而且，在目标成分的捕集量低的情况下，由于基质的存在而导致平衡状态崩解，难以准确地吸附。Furthermore, there is a disadvantage that the target component is decomposed due to the long-term consumption of heat. Furthermore, when the capture amount of the target component is low, the equilibrium state is broken due to the presence of the matrix, making accurate adsorption difficult.

另外，PDMS等的涂布只是在玻璃纤维或玻璃表面实施，表面积小。因此，能够保持的液相量有限，绝对回收率低。In addition, coating of PDMS etc. is only performed on the surface of glass fiber or glass, and the surface area is small. Therefore, the amount of liquid phase that can be maintained is limited, and the absolute recovery rate is low.

所以，本发明的目的在于，获得整体吸附件及利用其的吸附方法及装置，所述整体吸附件能够简易地用较短时间吸附极微量或低浓度的试样溶液，而且能够以少量的溶剂或短时间的加热来萃取保持成分，极其容易地确保分析所需的试样。Therefore, the object of the present invention is to obtain a monolithic adsorbent and an adsorption method and device using the same. The monolithic adsorbent can easily absorb a very small amount or a low-concentration sample solution in a relatively short period of time, and can absorb a small amount of solvent Or short-term heating to extract the retained components, making it extremely easy to ensure the sample required for analysis.

另外，本发明的目的还在于，获得比现有的固相萃取法中所使用的萃取材料吸附效率好的加热脱附、溶剂解吸效率好的可小型化的整体吸附件。In addition, the object of the present invention is to obtain a miniaturized monolithic adsorbent that is more efficient in thermal desorption and solvent desorption than the extraction material used in the conventional solid phase extraction method.

发明内容 Contents of the invention

作为解决上述课题用的手段，本发明提供整体吸附件，其特征在于，使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部，同时将化学物质涂布或化学结合在该结构体上。As means for solving the above-mentioned problems, the present invention provides a monolithic adsorbent, which is characterized in that the monolithic structure contains an adsorbent, and the adsorbent is exposed on the surface of the structure, and a chemical substance is coated or chemically bonded to the surface of the structure. on the structure.

另外，提供整体吸附件，其特征在于，所述吸附材料是选自石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合。In addition, an integral adsorbent is provided, wherein the adsorbent is selected from graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina , a mixture of one or more of florisil.

另外，提供整体吸附件，其特征在于，将具有疏水性乃至亲水性的化学物质化学结合在所述整体结构体表面。In addition, a monolithic adsorbent is provided, which is characterized in that a hydrophobic or even hydrophilic chemical substance is chemically bonded to the surface of the monolithic structure.

还有，提供一种整体吸附件，其特征在于，使树脂涂布乃至化学结合在所述整体结构体表面。In addition, there is provided a monolithic adsorbent characterized in that a resin is coated or chemically bonded to the surface of the monolithic structure.

另外，提供整体吸附件，其特征在于，进而使树脂涂布乃至化学结合在所述利用具有疏水性乃至亲水性的化学物质进行了表面处理的所述整体结构体上。In addition, an integral adsorbent is provided, which is characterized in that resin coating and chemical bonding are carried out on the surface with hydrophobic or even hydrophilic chemical substances. on the overall structure.

另外，提供整体吸附件，其特征在于，所述具有疏水性的化学物质含有具有选自十八烷基、甲基、乙基、辛基、环己基、乙烯基、苯基中的官能团的一种或多种的化合物。In addition, an integral adsorbent is provided, wherein the hydrophobic chemical substance contains a functional group selected from octadecyl, methyl, ethyl, octyl, cyclohexyl, vinyl, and phenyl. one or more compounds.

另外，提供整体吸附件，其特征在于，所述具有亲水性的化合物是具有选自二醇基、氰丙基、乙基羧基、磺酸基丙基、丙基苯磺酸基、氨基丙基、乙二胺-N-丙基、三甲基氨基丙基、聚酰胺基中的官能团的一种或多种的化合物。In addition, a monolithic adsorbent is provided, characterized in that the hydrophilic compound is selected from the group consisting of diol group, cyanopropyl group, ethyl carboxyl group, sulfonate propyl group, propylbenzenesulfonate group, aminopropyl group A compound of one or more functional groups in the group, ethylenediamine-N-propyl group, trimethylaminopropyl group, polyamide group.

另外，提供整体吸附件，其特征在于，所述树脂含有选自具有硅氧烷骨架的树脂、具有亲水性的树脂、具有疏水性的树脂中的一种或多种的混合物。In addition, there is provided a monolithic adsorbent characterized in that the resin contains one or more of a mixture selected from a resin having a siloxane skeleton, a hydrophilic resin, and a hydrophobic resin.

另外，提供整体吸附件，其特征在于，所述具有硅氧烷骨架的树脂含有选自聚二甲基硅氧烷、硅亚苯基硅氧烷(silphenylenesiloxane)、二苯基硅氧烷、氰丙基苯基硅氧烷、氰丙基硅氧烷中的一种或多种的混合物。In addition, there is provided a monolithic adsorbent, wherein the resin having a siloxane skeleton contains polydimethylsiloxane, silphenylenesiloxane, diphenylsiloxane, cyanide, A mixture of one or more of propylphenylsiloxane and cyanopropylsiloxane.

另外，提供整体吸附件，其特征在于，所述具有亲水性的树脂含有选自聚乙二醇、聚对苯二甲酸乙二醇酯、聚丙烯、二醇、碳蜡、聚丙烯酸、多元胺中的一种或多种的混合物。In addition, an integral adsorbent is provided, characterized in that the hydrophilic resin contains polyethylene glycol, polyethylene terephthalate, polypropylene, diol, carbowax, polyacrylic acid, multi-component One or more mixtures of amines.

另外，提供一种整体吸附件，其特征在于，所述具有疏水性的物质含有选自二乙烯基苯共聚物、苯乙烯共聚物、丙烯共聚物中的一种或多种的混合物。In addition, there is provided a monolithic adsorbent, wherein the hydrophobic substance contains one or more mixtures selected from divinylbenzene copolymers, styrene copolymers, and propylene copolymers.

另外，提供试样吸附方法，其特征在于，在收纳有液体或气体试样的容器内，收纳整体吸附件，使其浸渍于试样中，所述整体吸附件的构成为：使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部，同时对该结构体进行表面处理。In addition, a sample adsorption method is provided, which is characterized in that a monolithic adsorbent is accommodated in a container containing a liquid or a gas sample and immersed in the sample, and the monolithic adsorbent is configured such that the monolithic structure The adsorption material is contained, and the adsorption material is exposed on the surface of the structure, and the surface of the structure is treated at the same time.

另外，提供试样吸附方法，其特征在于，在收纳有液体或气体试样的容器内，收纳整体吸附件，搅拌试样和该整体吸附件，使其吸附试样中的目标成分，所述整体吸附件的构成为：使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部，同时对该结构体进行表面处理。In addition, a sample adsorption method is provided, which is characterized in that a monolithic adsorbent is accommodated in a container containing a liquid or gas sample, and the sample and the monolithic adsorbent are stirred to allow the target component in the sample to be adsorbed, said The monolithic adsorbent is constituted by making the monolithic structure contain the adsorbent, exposing the adsorbent on the surface of the structure, and simultaneously treating the surface of the structure.

另外，提供试样吸附方法，其特征在于，在收纳有气体试样的容器内，收纳整体吸附件，进行被动采样，所述整体吸附件的构成为，使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部，同时对该结构体进行表面处理。In addition, a sample adsorption method is provided, which is characterized in that a monolithic adsorbent is housed in a container containing a gas sample to perform passive sampling, and the monolithic adsorbent is configured such that the monolithic structure contains an adsorbent, and The adsorption material is exposed on the surface of the structure, and at the same time, the surface of the structure is treated.

另外，提供试样吸附方法，其特征在于，将收纳有整体吸附件的管插入容器气相部，同时，从容器外部通过容器盖将He、N2等惰性气体吹入试样中，使试样中的目标成分向容器气相部移动，保持在所述整体吸附件上，所述整体吸附件的构成为：使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部，同时对该结构体进行表面处理。In addition, a sample adsorption method is provided, which is characterized in that the tube containing the integral adsorption member is inserted into the gas phase part of the container, and at the same time, an inert gas such as He or N2 is blown into the sample from the outside of the container through the container cover to make the sample The target component in the container moves to the gas phase part of the container and is held on the integral adsorbent. The integral adsorbent is composed of: the integral structure contains the adsorbent material, and the adsorbent material is exposed on the surface of the structure. The structure is surface treated.

另外，提供试样吸附装置，其特征在于，在液体或气体试样的收纳容器或通道上，设有具有整体结构体的过滤器和整体吸附件，所述整体吸附件的构成为：使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部、同时对该结构体进行表面处理。In addition, a sample adsorption device is provided, which is characterized in that a filter with an integral structure and an integral adsorption piece are provided on a storage container or channel for a liquid or gas sample, and the integral adsorption piece is configured to make the whole The structure contains the adsorbent, and the surface of the structure is treated while exposing the adsorbent to the surface of the structure.

另外，提供试样吸附装置，其特征在于，将所述过滤器形成为容器形，将用于吸附目标成分的所述整体吸附件设置在其内部。In addition, there is provided a sample adsorption device characterized in that the filter is formed in a container shape, and the monolithic adsorption member for adsorbing a target component is provided inside it.

另外，提供试样吸附装置，其特征在于，使形成的所述过滤器中的所述整体结构体的通孔大于所述整体吸附件。In addition, there is provided a sample adsorption device characterized in that the through holes of the monolithic structure in the filter are formed larger than the monolithic adsorption material.

另外，提供试样吸附装置，其特征在于，使所述过滤器中的所述整体结构体通过亲水性乃至疏水性化合物或者离子性官能团进行反应。In addition, there is provided a sample adsorption device characterized in that the monolithic structure in the filter is reacted with a hydrophilic or hydrophobic compound or an ionic functional group.

另外，提供试样吸附装置，其特征在于，将整体吸附件配置在旋转搅拌器上，通过该搅拌器的旋转使目标成分吸附在该整体吸附件上，所述整体吸附件的构成为：使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面，同时对该结构体进行表面处理。In addition, a sample adsorption device is provided, which is characterized in that the integral adsorbent is arranged on a rotary stirrer, and the target component is adsorbed on the integral adsorbent by the rotation of the stirrer, and the integral adsorbent is configured such that The integral structure contains the adsorption material, and the adsorption material is exposed on the surface of the structure, and the surface of the structure is treated at the same time.

另外，提供试样吸附装置，其特征在于，在液体或气体试样中的目标成分的吸附或萃取中，将整体吸附件安装在可密合的容器内，由此可提高试样接触效率，所述整体吸附件的构成为：使整体结构体含有吸附材料，且使吸附材料暴露在该结构体表面部，同时对该结构体进行表面处理。In addition, a sample adsorption device is provided, which is characterized in that, in the adsorption or extraction of a target component in a liquid or gas sample, the integral adsorption member is installed in a sealable container, thereby improving the sample contact efficiency, The monolithic adsorbent is constituted by making the monolithic structure contain the adsorbent, exposing the adsorbent on the surface of the structure, and simultaneously treating the surface of the structure.

虽然本发明与SPME或SBSE是相同体积的固定相，但是通过作成整体结构体，固定相本身的厚度变薄，表面积增大，其结果，可用较短时间捕集(达到平衡状态)、萃取(脱附)。Although the present invention is a stationary phase of the same volume as SPME or SBSE, by making a monolithic structure, the thickness of the stationary phase itself becomes thinner and the surface area increases. As a result, trapping (reaching equilibrium), extraction ( desorption).

除此之外，具有暴露在整体吸附件的表面部的吸附材料的效果和在整体结构体表面部ODS(十八烷基硅烷)、SDB(苯乙烯二乙烯基苯共聚物)或二醇等疏水性乃至亲水性化合物进行反应的效果的协同效果，根据情况进而实施将树脂PDMS(聚二甲基硅氧烷)、PEG(聚乙二醇)等涂布在整个整体吸附件上等的表面处理，由此能够增加吸附能力。In addition, it has the effect of the adsorption material exposed on the surface of the monolithic adsorbent and ODS (octadecylsilane), SDB (styrene divinylbenzene copolymer) or glycol, etc. on the surface of the monolithic structure. The synergistic effect of the effect of the reaction of hydrophobic or hydrophilic compounds, and depending on the situation, the resin PDMS (polydimethylsiloxane), PEG (polyethylene glycol), etc. are applied to the entire adsorption material. Surface treatment, whereby the adsorption capacity can be increased.

另外，由于是整体结构体，因此，因具有连续的孔结构和具有许多介孔，故表面积大，目标溶液中的试样成分与吸附材料及ODS等烷氧基硅烷系试样的接触面积大，所以增加了吸附能力。In addition, because it is a monolithic structure, it has a continuous pore structure and many mesopores, so the surface area is large, and the contact area between the sample components in the target solution and the adsorption material and ODS and other alkoxysilane samples is large. , so the adsorption capacity is increased.

利用如上所述的表面积、吸附材料、疏水性乃至亲水性化合物、试剂等的协同效果，可进一步改善对试样的吸附。Adsorption to the sample can be further improved by utilizing the synergistic effect of surface area, adsorption material, hydrophobic or even hydrophilic compound, reagent, etc. as described above.

洗提PDMS等所保持的试样成分时，用于通过相平衡进行解吸的表面积少的现有方法不理想。相对于现有方法，本方法因为整体吸附件表面积大，所以洗提时与脱附气体或溶剂的接触面积大，能解吸非常少量的气体或溶剂的溶质成分。When eluting sample components held by PDMS or the like, the conventional method, which has a small surface area for desorption by phase equilibrium, is not ideal. Compared with the existing method, this method has a large surface area of the overall adsorbent, so it has a large contact area with the desorbed gas or solvent during elution, and can desorb a very small amount of solute components of the gas or solvent.

另外，表面积大和吸附能力改善意味着整体吸附件本身的小型化，特别是在GC、LC分析中具有重要意义。例如，如果在现行的GC自动进样器样品瓶中收纳本发明吸附件，则可以用少量的溶剂解吸，直接用自动进样器进行自动分析，可非常简易、廉价地进行浓缩分析。In addition, the large surface area and improved adsorption capacity mean the miniaturization of the overall adsorbent itself, which is of great significance especially in GC and LC analysis. For example, if the adsorbent of the present invention is accommodated in an existing GC autosampler vial, a small amount of solvent can be used for desorption, and the autosampler can be directly used for automatic analysis, and concentrated analysis can be performed very simply and cheaply.

在对环境水等进行浓缩分析的情况下，有时混合在环境水中的基质成分对于目标试样有干扰。现行的方法是通过预先过滤等除去干扰成分后进行浓缩，但该工序大多费时、繁琐。In the case of concentrated analysis of environmental water or the like, matrix components mixed in the environmental water may interfere with the target sample. The current method is to remove interfering components by pre-filtration and then concentrate, but this process is often time-consuming and cumbersome.

然而，本方法可一次性完成除去其干扰成分和只对目标试样选择性吸附、保持。在盖部的整体结构体中除去基质，进而在内部吸附整体材料中只选择性吸附目标试样。However, this method can remove its interfering components and only selectively adsorb and maintain the target sample at one time. The matrix is removed from the monolithic structure of the cover, and only the target sample is selectively adsorbed in the interior adsorption monolith.

另外，将Disk状(盘状)的基质除去机构50(相当于上述盖部)、整体吸附件51可粘贴地设置在容器内也可得到同样效果(图29)。In addition, the same effect can also be obtained by adhering a Disk-shaped (disk-shaped) matrix removing mechanism 50 (corresponding to the above-mentioned cover portion) and an integral adsorption member 51 in the container ( FIG. 29 ).

通过向本发明整体吸附件正确地通入试样溶液，可得到吸附量及吸附时间、吸附的简易性(数次抽吸)更加提高的效果。通过将用于萃取目标成分的溶剂也同样通入，用少量的溶剂即可产生回收效果，结果可在高浓度下进行分析。By accurately passing the sample solution into the monolithic adsorbent of the present invention, it is possible to further improve the adsorption capacity, adsorption time, and ease of adsorption (several times of suction). By passing the solvent used to extract the target component in the same way, the recovery effect can be produced with a small amount of solvent, and as a result, analysis can be performed at a high concentration.

另外，在热萃取中，产生缩短萃取时间的效果。利用这些效果，还产生如下效果：可得到色谱中的尖锐的峰，目标成分的热负荷受到抑制，可在不受基质存在的影响的条件下得到充分的吸附量。In addition, in hot extraction, there is an effect of shortening the extraction time. Utilizing these effects also produces the effect that a sharp peak in the chromatogram can be obtained, the thermal load of the target component can be suppressed, and a sufficient amount of adsorption can be obtained without being affected by the presence of the matrix.

另外，利用本发明的整体吸附件，可将用该整体吸附件吸附的试样用溶剂、热洗提并直接导入分析装置，可省去象现有方法那样在容器中洗提试样并送到注入口的麻烦，可用少量的溶剂脱附，另外，也有加热脱附容易的效果。In addition, by using the integral adsorbent of the present invention, the sample adsorbed by the integral adsorbent can be eluted with solvent and heat and directly introduced into the analysis device, which can save the need for eluting the sample in the container and sending it to the analyzer as in the existing method. Trouble to the injection port, it can be desorbed with a small amount of solvent, and also has the effect of easy desorption by heating.

在本发明的装置、方法中，即使在大量流过低浓度的试样的情况下，目标试样也不会从吸附件中流出(穿透、突破)，能够可靠地保持试样。结构体没有破损，能够可靠地保持试样。In the device and method of the present invention, even when a large amount of a low-concentration sample flows through, the target sample does not flow out (breakthrough, break through) from the adsorbent, and the sample can be reliably held. The structure was not damaged, and the sample could be reliably held.

在本发明中，对于试样而言，液体或气体均可使用，作为液体试样，可以应用于抽吸、浸渍、溶液中的搅拌、顶空分析、动态顶空分析、搅拌器等，作为气体试样，可以应用于主动采样器、被动采样器等。In the present invention, for the sample, liquid or gas can be used, and as a liquid sample, it can be applied to suction, immersion, stirring in a solution, headspace analysis, dynamic headspace analysis, stirrer, etc., as Gas samples can be applied to active samplers, passive samplers, etc.

附图说明 Description of drawings

图1是含活性炭整体结构体的脱附性能比较图，图2是本发明一实施例的立体图，图3是本发明一实施例的一制成状态说明图，图4是本发明一实施例的增塑剂分析色谱图，图5是本发明一实施例的挥发性有机物分析色谱图，图6是本发明一实施例的四氯化碳分析色谱图，图7是本发明一实施例的四氯化碳分析色谱图，图8是本发明一实施例的保持试样色谱图，图9是本发明一实施例的保持试样色谱图，图10是本发明一实施例的保持试样色谱图，图11是本发明一实施例的保持试样色谱图，图12是本发明一实施例的保持试样色谱图，图13是本发明一实施例的保持试样色谱图，图14是本发明一实施例的保持试样色谱图，图15是本发明实施例保持比较色谱图，图16是本发明实施例的保持比较色谱图，图17是本发明一实施例的使用状态说明图，图18是本发明一实施例的使用状态说明图，图19是本发明一实施例的使用状态说明图，图20是本发明一实施例的使用状态说明图，图21是本发明一实施例的使用状态说明图表，图22是本发明一实施例的使用状态效果说明图表，图23是本发明的一实施例和目标样品的回收率比较图，图24是本发明一实施例的江河分析色谱图，图25是本发明一实施例的江河分析色谱图，图26是本发明一实施例的室内化学物质分析色谱图，图27是本发明一实施例的室内化学物质分析色谱图，图28是本发明一实施例的概略说明图，图29是本发明其他实施例的概略说明图，图30是本发明一实施例的色谱图，图31是本发明一实施例的色谱图，图32是本发明一实施例的色谱图，图33是本发明一实施例的色谱图，图34本发明一实施例的色谱图，图35是本发明一实施例的色谱图，图36是根据本发明的采样效果图，图37是根据本发明的采样效果图，图38是本发明和目标样品的回收比较图，图39是本发明一实施例的吸附率和吸附时间的关系图，图40是本发明一实施例的温度和回收率的比较图，图41是本发明一实施例的盐析效果比较图，图42是本发明一实施例的平衡比较图，图43是本发明一实施例的平衡比较图，图44是本发明一实施例的与pH的关系图，图45是本发明一实施例的超声波照射比较图，图46是本发明一实施例的溶剂关系图，图47是本发明一实施例的吸附材料的性能试验图，图48是本发明一实施例的吸附材料的吸附比较图，图49是本发明一实施例的吸附材料的吸附比较图。Fig. 1 is a desorption performance comparison diagram of an integrated structure containing activated carbon, Fig. 2 is a perspective view of an embodiment of the present invention, Fig. 3 is an explanatory diagram of a manufacturing state of an embodiment of the present invention, and Fig. 4 is an embodiment of the present invention Plasticizer analysis chromatogram, Fig. 5 is the volatile organic compound analysis chromatogram of an embodiment of the present invention, Fig. 6 is the carbon tetrachloride analysis chromatogram of an embodiment of the present invention, Fig. 7 is the chromatogram of an embodiment of the present invention Carbon tetrachloride analysis chromatogram, Fig. 8 is the retention sample chromatogram of an embodiment of the present invention, Fig. 9 is the retention sample chromatogram of an embodiment of the present invention, Fig. 10 is the retention sample chromatogram of an embodiment of the present invention Chromatogram, Fig. 11 is the sample chromatogram of one embodiment of the present invention, Fig. 12 is the sample chromatogram of one embodiment of the present invention, Fig. 13 is the sample chromatogram of one embodiment of the present invention, Fig. 14 It is a sample chromatogram kept in an embodiment of the present invention. Figure 15 is a comparative chromatogram maintained in an embodiment of the present invention. Figure 16 is a comparative chromatogram maintained in an embodiment of the present invention. Figure 18 is an explanatory diagram of the use state of an embodiment of the present invention, Figure 19 is an explanatory view of the use state of an embodiment of the present invention, Figure 20 is an explanatory view of the use state of an embodiment of the present invention, and Figure 21 is an explanatory view of the use state of an embodiment of the present invention The use state description chart of the embodiment, Fig. 22 is the use state effect description chart of an embodiment of the present invention, Fig. 23 is the comparison figure of the recovery rate of an embodiment of the present invention and target sample, Fig. 24 is the recovery ratio of an embodiment of the present invention River analysis chromatogram, Fig. 25 is the river analysis chromatogram of one embodiment of the present invention, Fig. 26 is the indoor chemical substance analysis chromatogram of one embodiment of the present invention, Fig. 27 is the indoor chemical substance analysis chromatogram of one embodiment of the present invention , Figure 28 is a schematic illustration of an embodiment of the present invention, Figure 29 is a schematic illustration of other embodiments of the present invention, Figure 30 is a chromatogram of an embodiment of the present invention, Figure 31 is a chromatogram of an embodiment of the present invention , Fig. 32 is a chromatogram of an embodiment of the present invention, Fig. 33 is a chromatogram of an embodiment of the present invention, Fig. 34 is a chromatogram of an embodiment of the present invention, Fig. 35 is a chromatogram of an embodiment of the present invention, Fig. 36 It is a sampling effect diagram according to the present invention, Fig. 37 is a sampling effect diagram according to the present invention, Fig. 38 is a recovery comparison diagram of the present invention and the target sample, and Fig. 39 is a relationship diagram between adsorption rate and adsorption time of an embodiment of the present invention , Fig. 40 is a comparison diagram of temperature and recovery rate of an embodiment of the present invention, Fig. 41 is a comparison diagram of salting-out effect of an embodiment of the present invention, Fig. 42 is a balance comparison diagram of an embodiment of the present invention, and Fig. 43 is a comparison diagram of this invention The balance comparison diagram of an embodiment of the invention, Figure 44 is a relationship diagram with pH of an embodiment of the invention, Figure 45 is a comparison diagram of ultrasonic irradiation of an embodiment of the invention, and Figure 46 is a solvent relationship diagram of an embodiment of the invention , FIG. 47 is a performance test diagram of an adsorbent material according to an embodiment of the present invention, FIG. 48 is an adsorption comparison diagram of an adsorbent material according to an embodiment of the present invention, and FIG. 49 is an adsorption comparison diagram of an adsorbent material according to an embodiment of the present invention.

具体实施方式 Detailed ways

下面对本发明进行详细说明。作为用作整体吸附件时的表面积和通孔尺寸，通常使用范围如下。The present invention will be described in detail below. As the surface area and through-hole size when used as a monolithic adsorbent, the following ranges are generally used.

表面积自100m2/g至理想1000m2/g(实际350m2/g左右)，Surface area from 100m 2 /g to ideal 1000m 2 /g (actually about 350m 2 /g),

通孔尺寸1μm至100μm为宜，The size of the through hole is preferably 1 μm to 100 μm,

用作预过滤器时，When used as a pre-filter,

表面积为10m2/g以下，The surface area is 10m 2 /g or less,

通孔尺寸1μm至100μm为宜。The via hole size is preferably 1 μm to 100 μm.

在本发明中，优选按下述条件实施，但并不限定于此。In the present invention, it is preferable to implement under the following conditions, but it is not limited thereto.

关于活性炭About Activated Carbon

粒径：3～10μmParticle size: 3～10μm

表面积：800m2/gSurface area: 800m 2 /g

微孔容积：0.500cc/gMicropore volume: 0.500cc/g

微孔径：24.00 Micropore diameter: 24.00

关于整体结构体About the overall structure

通孔尺寸：5～15μmThrough hole size: 5～15μm

关于整体吸附件About Integral Snaps

吸附材料含量：1.5～3％Adsorbent material content: 1.5～3%

表面积：600～700m2 Surface area: 600～700m 2

一般认为，整体吸附件10是一种筒状体(a)：用多孔质体形成细长的筒状体11，上端形成开口12，在下端形成底部13，从而具有收纳部14，所述多孔质体是作为所谓整体结构体所知的三维网眼结构的具有连续的贯通孔的单一的结构体。此外，根据后来的嵌入形状，也可以选择盘状体(Disk状)半管状体等形式。(图2)It is generally believed that the integral adsorbent 10 is a cylindrical body (a): an elongated cylindrical body 11 is formed with a porous body, an opening 12 is formed at the upper end, and a bottom 13 is formed at the lower end, thereby having a receiving portion 14. A plastid is a single structure having continuous through-pores of a three-dimensional network structure known as a so-called bulk structure. In addition, depending on the subsequent embedding shape, forms such as a disk-shaped body (disk-shaped) and a semi-tubular body can also be selected. (figure 2)

作为该整体结构体，优选具有微孔、连续且规则整齐地形成网眼结构的结构体，但并不限定于此。As the overall structure, a structure having micropores and continuously and regularly forming a network structure is preferable, but it is not limited thereto.

进而，在吸附时，为了固定整体吸附件，也可考虑其中心具有贯通孔的形状。在其贯通孔内，插入由金属或树脂构成的棒进行固定，所述棒嵌入了端面经弯曲加工的材料或直径大的管等。Furthermore, it is conceivable to have a shape having a through hole at the center in order to fix the integral adsorption material during adsorption. In the through hole, a rod made of metal or resin is inserted and fixed, and the rod is fitted with a material with a bent end surface or a pipe with a large diameter.

在本发明中所使用的多孔质体是具有如下所述的细孔、具有所谓整体结构的多孔质体，其细孔为自上端至下端连通的结构。而且，优选细孔的轴向截面为圆形或接近圆形的材料，多孔质体的材质没有特别限制，但优选多孔质陶瓷、多孔质玻璃等无机质的多孔质体，例如多孔质玻璃。作为多孔质陶瓷的例子，有二氧化硅或钛、锆、铪等IVB族元素的化合物；硅酸铝质A(将硬磁器颗粒烧结而成的物质)、硅砂质、氧化铝质、铝硅酸盐质B(将耐火粘土颗粒烧结而成的物质)、多孔质莫来石质、硅藻土质的材料等。The porous body used in the present invention has pores as described below and has a so-called monolithic structure, and its pores are a structure that communicates from the upper end to the lower end. Furthermore, the axial cross-section of the pores is preferably circular or nearly circular. The material of the porous body is not particularly limited, but inorganic porous bodies such as porous ceramics and porous glass are preferred, such as porous glass. Examples of porous ceramics include silicon dioxide or compounds of Group IVB elements such as titanium, zirconium, and hafnium; aluminum silicate A (made by sintering hard magnetic particles), silica sand, alumina, aluminum silicon Salt material B (a material obtained by sintering refractory clay particles), porous mullite material, diatomaceous earth material, etc.

作为多孔质玻璃的例子，可举出组成为NaO-B2O3-SiO2-CaO系的物质，有时也用添加了Al2O3、ZrO2、ZnO2、TiO2、SnO2、MgO2等各种氧化物的玻璃制造。提案有一种利用由硼硅酸玻璃的热处理产生的相分离现象，使其取得互相缠绕的相分离结构后，对其中一个相进行酸洗提，由此来制造多孔质玻璃的方法。例如，将硅砂、硼酸、纯碱及氧化铝混合，在1200～1400℃熔融。将其在800～1100℃成型后，得到没有相分离的硼硅玻璃，通过热处理使SiO2相和B2O3-Na2O-CaO相进行相分离，通过酸处理制造残留有SiO2骨架的多孔质体。对细孔直径而言，通过根据用途改变热处理时的条件，可根据用途制造0.1～10微米的细孔分布均匀的材料。多孔质陶瓷可如下所述来制造，例如，将一定范围的粒径的陶瓷颗粒(硬磁粉粉碎物、硅石、氧化铝、耐火粘土等)和气孔形成材料、例如结晶纤维素(旭化成：Apicella)和适当的分散溶剂混合、成型、烧结。可根据用途制造细孔直径为500μ左右～0.1μ左右或超出其范围的细孔分布均匀的材料。Examples of porous glass include materials with a composition of NaO-B 2 O 3 -SiO 2 -CaO, sometimes with addition of Al 2 O 3 , ZrO 2 , ZnO 2 , TiO 2 , SnO 2 , MgO 2 and other glass manufacturing of various oxides. A method of producing porous glass is proposed by taking advantage of the phase separation phenomenon caused by heat treatment of borosilicate glass to obtain an intertwined phase separation structure, and then acid-eluting one of the phases. For example, silica sand, boric acid, soda ash and alumina are mixed and melted at 1200-1400°C. After molding it at 800-1100°C, borosilicate glass without phase separation is obtained. The SiO 2 phase and the B 2 O 3 -Na 2 O-CaO phase are separated by heat treatment, and the SiO 2 skeleton remains in the production by acid treatment. of porous bodies. Regarding the pore diameter, by changing the conditions of the heat treatment according to the application, a material with uniform distribution of pores of 0.1 to 10 microns can be produced according to the application. Porous ceramics can be produced as follows, for example, by mixing ceramic particles (hard magnetic powder pulverized material, silica, alumina, refractory clay, etc.) with a certain range of particle diameters and a pore-forming material such as crystalline cellulose (Asahi Kasei: Apicella) Mix with appropriate dispersing solvent, shape and sinter. According to the application, it is possible to produce a material with uniform distribution of pores with a pore diameter of about 500 μ to about 0.1 μ or beyond.

对上述微孔而言，应用适合于现有的填充剂所使用的分离试样的涂布剂及/或化学修饰剂，能够对细孔的表面进行修饰、改性。作为涂布剂，可举出例如聚乙二醇、硅油等。另外，作为化学修饰剂，可举出三甲基氯硅烷(TMS)、二甲基正辛基氯硅烷、二甲基正十八烷基氯硅烷(ODS)等烷基氯硅烷、γ-氨基丙基三乙氧基硅烷等氨基烷氧基硅烷、其他环氧硅烷等各种硅烷处理剂等。进而，在表面修饰剂的修饰基上也可以键合蛋白质等高分子化合物或低分子化合物。The surface of the micropores can be modified and modified by applying a coating agent and/or a chemical modifier suitable for the separation sample used in the conventional filler to the above-mentioned micropores. As a coating agent, polyethylene glycol, silicone oil, etc. are mentioned, for example. In addition, examples of chemical modifiers include alkylchlorosilanes such as trimethylchlorosilane (TMS), dimethyl n-octylchlorosilane, dimethyl n-octadecylchlorosilane (ODS), γ-amino Various silane treatment agents such as aminoalkoxysilanes such as propyltriethoxysilane and other epoxysilanes. Furthermore, a high-molecular compound such as a protein or a low-molecular compound may be bonded to the modifying group of the surface modifying agent.

另外，除了上述多孔质体外，推荐使用在上述多孔质体的细孔内填充了具有微孔的多孔质体的结构的多孔质体。对此进行说明。In addition to the aforementioned porous body, it is recommended to use a porous body having a structure in which pores of the aforementioned porous body are filled with a porous body having micropores. Explain this.

使用于制成微观多孔质体的单体浸渍在具有宏观细孔的骨架体的宏观细孔内，利用预先加入的溶剂等，使其在宏观细孔内聚合，由此制成小于宏观细孔、具有开放结构、填充了具有微孔多孔质体、具有整体化结构的多孔质体。这种情况下，所谓用于制成微观多孔质体的单体，可以是有机、无机的任一种材料，如果是无机类，将盐酸等催化剂加入四乙氧基硅烷中，浸渍制备的溶胶后，使其老化，由此能够形成具有微孔的多孔质石英玻璃。The monomer used to make the microporous body is impregnated in the macroscopic pores of the skeleton body with macroscopic pores, and polymerized in the macroscopic pores by using the pre-added solvent, etc. , has an open structure, is filled with a porous body with micropores, and a porous body with an integrated structure. In this case, the so-called monomer used to make a microscopic porous body can be any material, organic or inorganic. If it is inorganic, add a catalyst such as hydrochloric acid to tetraethoxysilane, and impregnate the prepared sol After that, it is aged to form porous silica glass having micropores.

另外，在有机类的情况下，可以选择各种树脂，使其浸渍例如丙烯酸酰胺单体后，使其聚合，由此可以得到聚丙烯酸酰胺凝胶多孔质体。但是，因为在所述的树脂中，不具有耐受加热之类的耐热性能，所以优选使用耐热的树脂。该微孔的范围可根据分离目标成分在液体中的分子大小来确定。对化学物质而言，当其处于液体中时，即使是蛋白质等具有高阶结构的物质，如果最大为1000nm，就会利用液体亲和力充分进入细孔内部。优选为100～500nm。In addition, in the case of organic resins, various resins can be selected, impregnated with, for example, acrylamide monomers, and then polymerized to obtain a polyacrylamide gel porous body. However, since the above-mentioned resins do not have heat resistance such as resistance to heating, it is preferable to use a heat-resistant resin. The range of the micropores can be determined according to the molecular size of the separation target component in the liquid. For chemical substances, when they are in a liquid, even substances with high-order structures such as proteins, if the maximum size is 1000nm, they will fully enter the interior of the pores by using the liquid affinity. Preferably it is 100 to 500 nm.

另一方面，还已知有利用作为液相反应的溶胶-凝胶法制成无机质多孔质体的方法。所谓溶胶-凝胶法，是指生成所谓的可聚合的低分子化合物，最终得到凝集物或聚合物的方法，可以采用如下方法。On the other hand, there is also known a method of producing an inorganic porous body by a sol-gel method which is a liquid phase reaction. The sol-gel method refers to a method of producing a so-called polymerizable low-molecular compound to finally obtain an aggregate or a polymer, and the following methods can be used.

具体方法是，将水溶性高分子或非离子性表面活性剂溶解在酸性水溶液中，在其中添加具有水解性的官能团的金属化合物进行水解反应，生成物固化后，接着进行干燥加热或溶剂置换的方法。利用的是均匀溶解的水溶性高分子或非离子性表面活性剂在金属醇盐或其低聚物的水解、聚合的过程中发生相分离的现象。The specific method is to dissolve a water-soluble polymer or a nonionic surfactant in an acidic aqueous solution, add a metal compound having a hydrolyzable functional group to carry out a hydrolysis reaction, and after the product is solidified, dry heating or solvent replacement is then carried out. method. What is used is the phenomenon that the homogeneously dissolved water-soluble polymer or nonionic surfactant undergoes phase separation during the hydrolysis and polymerization of metal alkoxides or their oligomers.

将非离子性表面活性剂、热分解性化合物溶解在酸性水溶液中，在其中添加具有水解性官能团的金属化合物进行水解反应，生成物固化后，接着加热湿润状态的凝胶，由此使制备凝胶时预先使其溶解的低分子化合物热分解，接着进行干燥加热。在此，作为金属醇盐或其低聚物，优选甲氧基、乙氧基、丙氧基等碳数少的物质。Dissolve nonionic surfactants and thermally decomposable compounds in acidic aqueous solution, add metal compounds with hydrolyzable functional groups to carry out hydrolysis reaction, and after the product is solidified, then heat the wet state gel to make the prepared gel When gluing, the low-molecular compound that has been dissolved in advance is thermally decomposed, followed by drying and heating. Here, metal alkoxides or oligomers thereof are preferably those having a small carbon number such as methoxy, ethoxy, and propoxy.

另外，作为其金属，通常使用最终形成的氧化物的金属，例如Si、Ti、Zr、Al。作为这种金属，可以是1种或2种以上。特别优选硅醇盐，作为硅醇盐，可以使用四甲氧基硅烷、四乙氧基硅烷、甲基三甲氧基硅烷、乙基三甲氧基硅烷、乙烯基三甲氧基硅烷，但并不限定于这些。In addition, as the metal, the metal of the finally formed oxide, such as Si, Ti, Zr, and Al, is usually used. As such metals, one type or two or more types may be used. Silicon alkoxide is particularly preferred. As silicon alkoxide, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane can be used, but not limited on these.

另一方面，作为低聚物，只要是能够均匀地溶解分散在醇中的物质即可，具体而言，可以使用至10聚体左右。优选以有机高分子相对于金属醇盐或其低聚物1重量份为0.03～0.40重量份的比例进行混合。On the other hand, any oligomer may be used as long as it can be uniformly dissolved and dispersed in alcohol, and specifically, up to about a decamer can be used. Preferably, the organic polymer is mixed in a ratio of 0.03 to 0.40 parts by weight relative to 1 part by weight of the metal alkoxide or its oligomer.

水溶性有机高分子只要是在水解的过程中发生相分离、均匀地溶解在通过金属醇盐或低聚物水解生成的醇盐或者是通过其低聚物水解生成的含醇的液体中的物质即可。具体而言，优选作为高分子金属盐的聚苯乙烯磺酸的钠盐、作为高分子酸的分解成为聚阴离子的ポリアイリル酸等、作为高分子碱的在水溶液中生成聚阳离子的聚烯丙胺及聚乙烯亚胺等或作为中性高分子的主链具有醚键的聚环氧乙烷等、侧链具有γ-内酰胺的聚乙烯吡咯烷酮等。Water-soluble organic polymers, as long as they undergo phase separation during hydrolysis and are uniformly dissolved in the alkoxide produced by the hydrolysis of metal alkoxides or oligomers, or in alcohol-containing liquids produced by the hydrolysis of their oligomers That's it. Specifically, sodium salt of polystyrenesulfonic acid as a polymer metal salt, polyaryl acid as a polymer acid decomposed into a polyanion, etc., polyallylamine and the like as a polymer base that generate polycations in an aqueous solution are preferred. Polyethyleneimine or the like, polyethylene oxide or the like having an ether bond in its main chain as a neutral polymer, or polyvinylpyrrolidone or the like having a γ-lactam in a side chain, or the like.

非离子性表面活性剂是具有同时引起溶胶-凝胶转移和相分离过程的作用的物质，由此，在分离成富溶剂相和骨架相的同时凝胶化。非离子性表面活性剂优选包含聚氧乙烯等亲水部和主要由烷基构成的疏水部的物质，例如聚氧乙烯壬苯基醚、聚氧乙烯辛苯基醚、聚氧乙烯烷基醚，作为亲水部包含聚氧丙烯的物质，例如聚氧丙烯烷基醚等，但并不限定于这些。添加的非离子性表面活性剂的量也受表面活性剂的种类、金属醇盐的种类、量的影响，相对于10g金属醇盐为1.0～10.0g、优选为1.5～6.0g。A nonionic surfactant is a substance that has an effect of causing both sol-gel transition and phase separation processes, thereby gelling while being separated into a solvent-rich phase and a skeleton phase. The nonionic surfactant preferably contains a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether , a substance containing polyoxypropylene as a hydrophilic part, such as polyoxypropylene alkyl ether, etc., but not limited to these. The amount of the nonionic surfactant to be added is also affected by the type and amount of the surfactant and the metal alkoxide, and is 1.0 to 10.0 g, preferably 1.5 to 6.0 g, per 10 g of the metal alkoxide.

当将非离子性表面活性剂、热分解性化合物溶解在酸性水溶液中，在其中添加具有水解性的官能团的金属化合物进行水解反应时，生成分离为富溶剂相和骨架相的凝胶。生成物(凝胶)固化后，经过适当的熟成时间后，加热湿润状态的凝胶，由此可使预先溶解在反应溶液中的热分解性化合物进行热分解，接触骨架相的内壁面的溶剂的pH值上升。When a nonionic surfactant or a thermally decomposable compound is dissolved in an acidic aqueous solution, and a metal compound having a hydrolyzable functional group is added thereto for a hydrolysis reaction, a gel separated into a solvent-rich phase and a skeleton phase is formed. After the product (gel) is solidified, after an appropriate aging time, the wet gel is heated to thermally decompose the pyrolytic compound previously dissolved in the reaction solution and contact the solvent on the inner wall surface of the skeleton phase. The pH rises.

于是，溶剂侵蚀其内壁面，可改变内壁面的凹凸状态，由此将细孔直径逐渐扩大。此时，作为所使用的酸性水溶液，通常优选盐酸、硝酸等矿酸0.001当量以上的酸。当水解时，通过将这样的溶液放入密闭容器中，在温度40～80℃保持0.5～5小时来完成。水解经过最初透明的溶液发生混浊而与有机高分子发生相分离、终于凝胶化的过程。在此水解过程中，有机高分子或其聚合物处于分散状态，实质上没有产生这些的沉淀。如此凝胶化的物质在40～80℃放置数小时～数十小时左右进行熟成后，用水清洗除去有机高分子，在800～1000℃左右煅烧得到多孔质玻璃。Then, the solvent erodes the inner wall surface to change the concave and convex state of the inner wall surface, thereby gradually expanding the diameter of the pores. In this case, as the acidic aqueous solution to be used, generally, an acid having 0.001 equivalent or more of mineral acid such as hydrochloric acid or nitric acid is preferable. When hydrolyzing, it is accomplished by putting such a solution in a closed container and keeping it at a temperature of 40-80° C. for 0.5-5 hours. Hydrolysis is a process in which the initially transparent solution becomes turbid, phase-separates from organic polymers, and finally gels. During this hydrolysis process, organic macromolecules or polymers thereof are in a dispersed state, and precipitation of these does not substantially occur. The gelled material is aged at 40-80°C for several to tens of hours, washed with water to remove organic polymers, and calcined at about 800-1000°C to obtain porous glass.

作为使整体吸附件自身含有的吸附材料，可举出活性炭、石墨碳、碳纳米管、富勒烯、分子筛、硅胶、沸石、硅藻土、二乙烯基苯共聚物(苯乙烯二乙烯基苯等)、碳分子筛、活性氧化铝、氟罗里硅土(硅酸镁)等。将这些吸附材料单独或数种混合，添加在溶胶-凝胶溶液中，使其均匀分散。As the adsorbent material contained in the monolithic adsorbent itself, activated carbon, graphitic carbon, carbon nanotube, fullerene, molecular sieve, silica gel, zeolite, diatomaceous earth, divinylbenzene copolymer (styrene divinylbenzene etc.), carbon molecular sieves, activated alumina, florisil (magnesium silicate), etc. These adsorbents are added alone or mixed together in a sol-gel solution to make them uniformly dispersed.

关于制法About the method

(吸附材料的添加)(addition of adsorption material)

在溶胶-凝胶溶液中，适量(0.1～20％)加入吸附材料(活性炭、分子筛、苯乙烯二乙烯基苯等树脂系吸附材料、石墨、沸石、硅藻土等)，用搅拌子·超声波清洗机搅拌，将该溶液适量迅速地流进模型。需要说明的是，加入所述溶液中之前，将上述吸附材料粉碎，尽量减小粒径成为提高吸附能力的因素之一。优选预先制成平均直径5μm以下。将活性炭等粉碎变细后，与分子筛或硅石等具有坚硬的性质的细颗粒一起混合，进行粉碎，由此可得到细颗粒。In the sol-gel solution, add an appropriate amount (0.1-20%) of adsorption materials (resin-based adsorption materials such as activated carbon, molecular sieves, styrene divinylbenzene, graphite, zeolite, diatomaceous earth, etc.), and use a stirrer · ultrasonic The washing machine stirs, and the solution flows into the model in an appropriate amount and quickly. It should be noted that, before adding to the solution, the above-mentioned adsorbent material is pulverized to reduce the particle size as much as possible, which is one of the factors for improving the adsorption capacity. Preferably, the average diameter is 5 μm or less in advance. Fine particles can be obtained by pulverizing activated carbon, etc., and mixing with hard fine particles such as molecular sieves or silica, and pulverizing.

另外，在该吸附材料中，上述分子筛或硅石等没有必要在以后除去，相反使之混合能够增强吸附能力。In addition, in this adsorbent, the above-mentioned molecular sieves, silica, etc. need not be removed later, and on the contrary, mixing them can enhance the adsorption capacity.

(凝胶化及固化处理)(Gelation and curing treatment)

在模型中装满溶胶-凝胶溶液并密闭，在适当温度的恒温箱中使其凝胶化(1小时～1天以上)。其后，将从模型中取出的整体结构体用纯水中和，浸渍在碱性水溶液(增多介孔时)或纯水(不需要作成介孔时)中，加热促进固化。Fill the mold with a sol-gel solution and seal it tightly, and gel it in an incubator at an appropriate temperature (1 hour to more than 1 day). Thereafter, the monolithic structure taken out of the model is neutralized with pure water, immersed in an alkaline aqueous solution (when mesopores are increased) or pure water (when mesopores are not required), and heated to accelerate curing.

(煅烧处理)(calcination treatment)

上述处理后，进行中和(纯水)、脱水、使其干燥。其后，将整体结构体放入金属管中，从一侧通入惰性气体(He、N2等)。After the above treatment, neutralization (pure water), dehydration, and drying are performed. Thereafter, the monolithic structure is placed in a metal tube, and an inert gas (He, N 2 , etc.) is passed through from one side.

(吸附材料的暴露工序)(Exposure process of adsorbent)

煅烧后，为了使许多吸附材料暴露在表面，浸渍在适当浓度的碱性水溶液(例如氢氧化钠、氢氧化钾、氨水)中，进行加热处理(40～200℃)。其后，进行中和(纯水)，使其干燥。After calcination, in order to expose many adsorption materials on the surface, it is immersed in an alkaline aqueous solution (such as sodium hydroxide, potassium hydroxide, ammonia water) of appropriate concentration, and heat-treated (40-200° C.). Thereafter, neutralization (pure water) was performed, followed by drying.

另外，除了上述方法以外，有时也用锉等研磨表面。In addition, in addition to the above methods, the surface may also be polished with a file or the like.

(整体结构体表面部的表面处理)(Surface treatment of the surface of the monolithic structure)

作为对整体结构体进行化学处理的方法，一般推荐进行亲水化和疏水化处理。As a method of chemically treating the bulk structure, hydrophilization and hydrophobization are generally recommended.

作为疏水化的方法，干燥后，进行酸处理、中和(纯水)，干燥后，使其浸渍在具有十八烷基、甲基、乙基、辛基、环己基、乙烯基、苯基等的烷氧基硅烷、氯硅烷等富于反应性的试剂中，通过热使其反应。各官能团单、二、三均可应用。As a method of hydrophobization, after drying, acid treatment and neutralization (pure water) are performed, and after drying, it is impregnated with octadecyl, methyl, ethyl, octyl, cyclohexyl, vinyl, phenyl Reactive reagents such as alkoxysilanes and chlorosilanes are reacted by heat. Single, two, and three functional groups can be applied.

例如，对于甲基而言，二甲基、三甲基或四甲基均可应用。反应后，用有机溶剂清洗、干燥，边通入惰性气体边加热。For example, for methyl, dimethyl, trimethyl or tetramethyl can be used. After the reaction, it is washed with an organic solvent, dried, and heated while passing an inert gas.

进而，为了提高疏水性，还推荐进行2次疏水化处理。通过实施该2次处理，能够提高惰性度，减少表面吸附。对于二次处理而言，在上述疏水性化合物中，十八烷基、辛基等侧链长时，有时不能彻底修饰表面，所以优选再次修饰。Furthermore, in order to improve the hydrophobicity, it is also recommended to perform a second hydrophobization treatment. By performing this secondary treatment, the degree of inertness can be increased and surface adsorption can be reduced. Regarding the secondary treatment, among the above-mentioned hydrophobic compounds, if the side chains such as octadecyl group and octyl group are long, the surface may not be completely modified, so re-modification is preferable.

此时，使其浸渍在包含侧链短的甲基、乙基、苯基、乙烯基的烷氧基硅烷试剂中，通过热使其反应。反应后，用有机溶剂清洗、干燥、边通入惰性气体边加热。At this time, it is immersed in an alkoxysilane reagent containing a methyl group, an ethyl group, a phenyl group, or a vinyl group with a short side chain, and reacted with heat. After the reaction, it is washed with an organic solvent, dried, and heated while passing an inert gas.

进而，通过重复操作，也可调整疏水性，但由于3次以后效果降低，因此推荐至2次处理。Furthermore, the hydrophobicity can also be adjusted by repeated operations, but since the effect decreases after 3 treatments, it is recommended to use 2 treatments.

通过上述疏水化，能够浮在水中，适于捕集水中的微量成分或选择性捕集疏水性化合物或高惰性等，也可通过变更结合基种类或次数调整疏水性等，根据目的进行处理。Through the above-mentioned hydrophobization, it can float in water and is suitable for trapping trace components in water or selectively trapping hydrophobic compounds or high inertness. It is also possible to adjust the hydrophobicity by changing the type or frequency of the binding group, etc., according to the purpose.

(整体结构体表面部的表面处理)(Surface treatment of the surface of the monolithic structure)

另外，作为亲水化的方法，干燥后，进行酸处理、中和(纯水)，干燥后，使其浸渍在具有二醇基、氰丙基、乙基羧基、磺酸基丙基、丙基苯磺酸基、氨基丙基、乙二胺-N-丙基、三甲基氨基丙基、聚酰胺基等亲水性的富于反应性的试剂中，通过热使其反应。反应后，用有机溶剂清洗，干燥，边通入惰性气体边加热。In addition, as a method of hydrophilization, acid treatment and neutralization (pure water) are performed after drying, and after drying, it is immersed in a surface having a glycol group, a cyanopropyl group, an ethyl carboxyl group, a sulfopropyl group, or a propyl group. Hydrophilic reactive reagents such as phenylsulfonic acid group, aminopropyl group, ethylenediamine-N-propyl group, trimethylaminopropyl group, polyamide group, etc., are reacted by heat. After the reaction, it is washed with an organic solvent, dried, and heated while blowing an inert gas.

这样，通过实施亲水性处理，可适于捕集油、汽油或己烷等非水性溶剂中的亲水性化合物的微量成分或选择性捕集亲水性化合物等。Thus, by performing the hydrophilic treatment, it is suitable for trapping trace components of hydrophilic compounds in non-aqueous solvents such as oil, gasoline, or hexane, or for selectively trapping hydrophilic compounds.

(整体结构体表面部的树脂的涂布·化学结合)(Coating and chemical bonding of resin on the surface of the monolithic structure)

进而，推荐在这些实施过疏水性乃至亲水性的化学处理的整体结构体的表面进一步实施涂布树脂或化学处理。Furthermore, it is recommended to further apply resin coating or chemical treatment to the surface of these monolithic structures that have undergone hydrophobic or even hydrophilic chemical treatment.

就树脂而言，作为具有硅氧烷骨架的树脂，有选自聚二甲基硅氧烷、硅亚苯基硅氧烷、二苯基硅氧烷、氰丙基苯基硅氧烷、氰丙基硅氧烷中的一种或多种的混合物。As for the resin, as the resin having a siloxane skeleton, there are polydimethylsiloxane, silylphenylene siloxane, diphenyl siloxane, cyanopropylphenyl siloxane, cyanide One or more mixtures of propyl siloxane.

作为具有亲水性的树脂，有选自聚乙二醇、聚对苯二甲酸乙二醇酯、聚丙烯、二醇、碳蜡、聚丙烯酸、多元胺中的一种或多种的混合物，具有疏水性的树脂有选自二乙烯基苯共聚物、苯乙烯共聚物、丙烯共聚物中的一种或多种的混合物。As a hydrophilic resin, there are one or more mixtures selected from polyethylene glycol, polyethylene terephthalate, polypropylene, diol, carbowax, polyacrylic acid, and polyamines, The hydrophobic resin has one or more mixtures selected from divinylbenzene copolymers, styrene copolymers, and propylene copolymers.

使整体结构体浸渍在用溶剂将上述树脂稀释到适当的浓度的溶液中，通过除去溶剂或热反应使其涂布乃至化学结合。由此，可以对整体结构体用树脂涂布乃至化学结合。The monolithic structure is dipped in a solution in which the above-mentioned resin is diluted to an appropriate concentration with a solvent, and coated or chemically bonded by solvent removal or thermal reaction. Thereby, resin coating and chemical bonding can be performed on the monolithic structure.

通过使树脂涂布乃至化学结合，整体结构体表面上的化学物质量增加，其结果，可使其更多地负载目标成分。By coating or chemically bonding the resin, the amount of the chemical substance on the surface of the monolithic structure increases, and as a result, the target component can be loaded more.

实际上，通过向整体结构体表面直接涂布树脂或化学结合，也可吸附目标成分。In fact, target components can also be adsorbed by direct coating of resins or chemical bonding to the surface of the monolith.

但是，在从包含基质的试样中选择性吸附时，一般推荐利用具有如上所述的亲水性或疏水性的化学物质进行处理后的树脂处理。However, in the case of selective adsorption from a sample containing a matrix, resin treatment after treatment with a chemical substance having either hydrophilic or hydrophobic properties as described above is generally recommended.

关于模型about the model

使用图3所示的模型，制成整体结构体。Using the model shown in Figure 3, a monolithic structure is made.

模型的基材使用亲水性树脂材料1(PEEK材料等)，在该树脂材料1上开设不贯通的孔2，将其末端制成圆锥形状3，加工成适合GC自动自动进样器样品瓶的形状，将树脂棒4配置在其中心，承接侧的末端部开设该棒的逸孔5。A hydrophilic resin material 1 (PEEK material, etc.) is used as the base material of the model, and a non-through hole 2 is opened in the resin material 1, and the end is made into a conical shape 3, and processed into a sample bottle suitable for GC automatic autosamplers The shape of the resin rod 4 is arranged in its center, and the end portion of the receiving side is opened with the escape hole 5 of the rod.

整体吸附件的形状不限于上述形状，可容易地制成适合目的用途的盘状、杆状、杯状等。The shape of the integral adsorbent is not limited to the above-mentioned shapes, and it can be easily made into a disk shape, rod shape, cup shape, etc. suitable for the intended use.

<实施例1><Example 1>

通过图1对仅有整体结构体和使该结构体含有活性炭的情况下的吸附的比较进行说明。A comparison of the adsorption between only the monolithic structure and the case where the structure contains activated carbon will be described with reference to FIG. 1 .

1)含活性炭的整体结构体(未进行ODS化·涂布处理)：实线1) Monolithic structure containing activated carbon (without ODSization and coating treatment): solid line

2)仅有整体结构体(未进行ODS化·涂布处理)：虚线2) Monolithic structure only (without ODSization and coating treatment): dotted line

(实验方法)(experimental method)

将整体吸附件1)及2)设置于5ml螺旋管的上部(顶部空间)(固定在气相部)，将挥发性有机化合物(25μg/mL)注入在该螺旋管内，将该管密封并放置10分钟，其后，将各个整体吸附件用100μL甲醇洗提，用1μLGCMS进行分析，求出面积值的比较值。The monolithic adsorbents 1) and 2) were placed on the upper part (headspace) of a 5 ml spiral tube (fixed in the gas phase part), and volatile organic compounds (25 μg/mL) were injected into the spiral tube, and the tube was sealed and left for 10 After that, each monolithic adsorbent was eluted with 100 μL of methanol, analyzed with 1 μL GCMS, and the comparative value of the area value was obtained.

在该试验中，设定活性炭的含量为1.5％(重量比)、粒径为3～10μm、通孔尺寸为5～10μm、整体吸附件的表面积为60～700m2/g。In this test, the content of activated carbon is 1.5% (by weight), the particle size is 3-10 μm, the through-hole size is 5-10 μm, and the surface area of the monolithic adsorbent is 60-700 m 2 /g.

(结果)(result)

使其含有活性炭时，可以看到整体性良好的回收效果。特别是在1，1-二氯乙烯～1，2-二氯乙烷(沸点达到32℃～83.5℃的低沸点成分)中，含活性炭的效果明显(图1)。When activated carbon is included, a good overall recovery effect can be seen. In particular, in 1,1-dichloroethylene to 1,2-dichloroethane (low-boiling components having a boiling point of 32°C to 83.5°C), the effect of containing activated carbon is remarkable (Fig. 1).

<实施例2><Example 2>

挥发性有机化合物试样的分析Analysis of Volatile Organic Compound Samples

实验方法experimental method

在40mL的水中，添加15％的盐，调整到2ppb/40mL的浓度。Add 15% salt to 40 mL of water, and adjust to a concentration of 2 ppb/40 mL.

将含有粒径10μm以下的活性炭的通孔5～15μm的整体硅石19.4mg放入容器中，搅拌10分钟。19.4 mg of monolithic silica containing activated carbon having a particle diameter of 10 μm or less and having through-holes of 5 to 15 μm was put into a container, and stirred for 10 minutes.

其后，用100μL甲醇萃取(萃取时间10分钟，施加超声波)。Thereafter, extraction was performed with 100 μL of methanol (extraction time 10 minutes, ultrasonic waves were applied).

取1μL萃取液，在不分流的条件下以GCMS、SIM模式进行分析。向GCMS的绝对注入量为0.8μg。Take 1 μL of the extract and analyze it in GCMS and SIM mode under splitless conditions. The absolute injection amount into GCMS was 0.8 μg.

(结果)(result)

如图5所示，得到了非常良好的效果。灵敏度也完全没有问题。As shown in Figure 5, very good results were obtained. Sensitivity is also no problem at all.

<实施例3><Example 3>

低浓度挥发性有机化合物试样的分析Analysis of Low Concentration Volatile Organic Compound Samples

低浓度0.2ppb(0.2μg/L)的四氯化氮的分析，在低浓度中，确认用本方法能否测出。For the analysis of nitrogen tetrachloride at a low concentration of 0.2ppb (0.2μg/L), it is confirmed whether it can be detected by this method at a low concentration.

(实验方法)(experimental method)

在40mL的水中，添加15％的盐，调整到0.2ppb/mL的浓度。15% of salt was added to 40 mL of water to adjust the concentration to 0.2 ppb/mL.

将含有粒径10μm以下的活性炭的通孔5～15μm的整体硅石22mg放入容器中，搅拌10分钟。22 mg of monolithic silica containing activated carbon having a particle size of 10 μm or less and having through-holes of 5 to 15 μm was put into a container, and stirred for 10 minutes.

其后，用100μL甲醇萃取。Thereafter, extraction was performed with 100 µL of methanol.

取1μL萃取液，在不分流的条件下以GCMS、SIM模式(selectedionmoniter)进行分析。向GCMS的绝对注入量为0.08ng。Take 1 μL of the extract and analyze it in GCMS, SIM mode (selectedionmoniter) under splitless conditions. The absolute injection amount into GCMS was 0.08ng.

(结果及研究)(Results and Research)

筛选性地接近极限，但可确认测出。(图6、图7)。Screening is close to the limit, but detectable with confirmation. (Figure 6, Figure 7).

要筛选性地判断是否测出，从本实验能够判断即使溶剂萃取也可以确认。当然，为了进一步提高精度、灵敏度，只要用加热脱附法实施，注入1μL即可以得到其100倍的灵敏度，具有充分的性能。To judge whether it is detected in a screening manner, it can be judged from this experiment that it can be confirmed even by solvent extraction. Of course, in order to further improve the accuracy and sensitivity, if it is implemented by the heating desorption method, injecting 1 μL can obtain 100 times the sensitivity, and it has sufficient performance.

<实施例4><Example 4>

在活性炭、石墨、只进行ODS处理的保持的比较中，用同浓度2ppb挥发性有机化合物的洗提量的比较试验的条件设定为：活性炭的粒径为10μm以下、石墨表面积大约为100m2/g、整体结构体的通孔尺寸为5～15μm。In the comparison of activated carbon, graphite, and only ODS treatment, the conditions of the comparative test of the elution amount of volatile organic compounds at the same concentration of 2ppb are set: the particle size of activated carbon is 10μm or less, and the surface area of graphite is about 100m 2 /g, and the through-hole size of the monolithic structure is 5-15 μm.

a.含活性炭硅石整体ODS处理a. Integral ODS treatment of silica containing activated carbon

b.含石墨硅石整体ODS处理b. Integral ODS treatment with graphite silica

c.硅石整体ODS处理c. Overall ODS treatment of silica

(试样1)(sample 1)

①：1，1-二氯乙烯、②：二氯甲烷、③：反式1，2-二氯乙烯在低沸点区域(上述3试样)中，活性炭的优势明显。(图8)①: 1,1-dichloroethylene, ②: dichloromethane, ③: trans-1,2-dichloroethylene In the low boiling point region (the above 3 samples), the advantage of activated carbon is obvious. (Figure 8)

(试样2)(sample 2)

①：顺式1，2-二氯乙烯、②：氯仿、③：1，1，1-三氯乙烷、④：四氯化碳、⑤：1，2-二氯乙烷、⑥：苯(图9)①: cis-1,2-dichloroethylene, ②: chloroform, ③: 1,1,1-trichloroethane, ④: carbon tetrachloride, ⑤: 1,2-dichloroethane, ⑥: benzene (Figure 9)

(试样3)(sample 3)

①：三氯乙烯、②：1，2-二氯丙烷、③：一溴二氯甲烷(图10)①: Trichloroethylene, ②: 1,2-dichloropropane, ③: Bromodichloromethane (Figure 10)

(试样4)(sample 4)

①：顺式1，3-二氯-1-丙烯、②：甲苯、③：反式1，3-二氯-1-丙烯、④：1，1，2-三氯乙烷、⑤：四氯乙烯、⑥：二溴一氯甲烷①: cis-1,3-dichloro-1-propene, ②: toluene, ③: trans-1,3-dichloro-1-propene, ④: 1,1,2-trichloroethane, ⑤: four Vinyl chloride, ⑥: Dibromochloromethane

在环状结构的甲苯中，可以确认含有石墨的保持不逊色于活性炭。如石墨碳的特性所示(图11)。In ring-structured toluene, it was confirmed that graphite-containing retention was not inferior to activated carbon. As shown by the properties of graphitic carbon (Fig. 11).

(试样5)(Sample 5)

①：间二甲苯、对二甲苯、②：邻二甲苯①: m-xylene, p-xylene, ②: o-xylene

可以确认环状结构强的石墨碳的保持强。(图12)It was confirmed that the retention of graphitic carbon with a strong ring structure is strong. (Figure 12)

(试样6)(Sample 6)

溴仿Bromoform

活性炭、石墨无差别。(图13)There is no difference between activated carbon and graphite. (Figure 13)

(试样7)(Sample 7)

1，4-二氯苯1,4-Dichlorobenzene

在环状中强的石墨碳的优势明显(图14)。The predominance of strong graphitic carbon is evident in the ring (Fig. 14).

就活性炭、石墨碳2种而言，分别有其特性，活性炭有利于低沸点成分，石墨有利于具有环状结构的成分，对于本挥发性有机化合物分析而言，可以预测以通过复式投注使2种混合为宜。As far as activated carbon and graphite carbon are concerned, each has its own characteristics. Activated carbon is beneficial to low-boiling components, and graphite is beneficial to components with a ring structure. For the analysis of volatile organic compounds, it can be predicted that 2 A mixture is appropriate.

只要根据目的在整体结构中混合某种吸附材料，就可以方便地制成符合目标之物，而且，因ODS的缘故而有防水性，徒劳的干燥清洗也可简便化，可以说是蕴藏了非常可能性的捕集方法。另外，由于具有作为整体结构的优点的通孔的结构，因此，试剂因容易通过吸附材料内部而容易吸附，由于溶剂也同样通过，因此，即使较少的溶剂量也能萃取。As long as some kind of adsorption material is mixed in the overall structure according to the purpose, it can be easily made into a product that meets the target. Moreover, because of the ODS, it is waterproof and simplifies useless dry cleaning. It can be said that it has great potential. Possibility of capture methods. In addition, due to the through-hole structure which is an advantage of the overall structure, the reagent is easily adsorbed by passing through the interior of the adsorbent, and since the solvent also passes through, it can be extracted even with a small amount of solvent.

<实施例5><Example 5>

挥发性有机化合物试样Volatile Organic Compound Sample

1，1-二氯乙烯、二氯甲烷、反式1，2-二氯乙烯、顺式1，2-二氯乙烯氯仿、1，1，1-三氯乙烷、四氯化碳、1，2-二氯乙烷苯、三氯乙烯、1，2-二氯丙烷、一溴二氯甲烷、顺式1，3-二氯-1-丙烯、甲苯、反式1，3-二氯-1-丙烯、1，1，2-三氯乙烷、四氯乙烯、二溴一氯甲烷、间二甲苯、对二甲苯、邻二甲苯、溴仿、1，4-二氯苯1,1-dichloroethylene, dichloromethane, trans-1,2-dichloroethylene, cis-1,2-dichloroethylene chloroform, 1,1,1-trichloroethane, carbon tetrachloride, 1 , 2-dichloroethanebenzene, trichloroethylene, 1,2-dichloropropane, bromodichloromethane, cis-1,3-dichloro-1-propene, toluene, trans-1,3-dichloro -1-propene, 1,1,2-trichloroethane, tetrachloroethylene, dibromochloromethane, m-xylene, p-xylene, o-xylene, bromoform, 1,4-dichlorobenzene

将上述各成分添加在添加15％NaCl的40mL水溶液中，调制为2ppb的浓度，在其水中放入下述的整体吸附件，搅拌30分钟。Each of the above-mentioned components was added to 40 mL of aqueous solution to which 15% NaCl was added to adjust to a concentration of 2 ppb, and the following monolithic adsorbent was placed in the water and stirred for 30 minutes.

1)整体结构体，用ODS处理过表面之物1) The overall structure, the surface of which has been treated with ODS

2)使整体结构体含有活性炭，用ODS处理过表面之物2) Make the whole structure contain activated carbon, and treat the surface with ODS

3)使整体结构体含有活性炭、石墨，用ODS处理过表面之物3) Make the overall structure contain activated carbon, graphite, and treat the surface with ODS

4)使整体结构体含有活性炭、石墨、分子筛，用ODS处理过表面之物4) Make the overall structure contain activated carbon, graphite, molecular sieve, and treat the surface with ODS

其后，取出上述整体吸附件，用100μL的溶剂洗提，以GCMS、SIM模式注入1μL。将各成分的绝对保持容量设定为40mL，因为80ng是所保持的计算之量，所以用100μL稀释，若注入1μL则为0.8ng。Thereafter, the monolithic adsorbent was taken out, eluted with 100 μL of solvent, and 1 μL was injected in GCMS, SIM mode. The absolute retention capacity of each component was set at 40 mL, and since 80 ng was the calculated amount to be retained, it was diluted with 100 μL, and 0.8 ng was injected into 1 μL.

因而，调整用于比较回收率的标准试样，使其1μL中为0.8ng，注入，得到面积值。Therefore, the standard sample for comparison of recoveries was adjusted so that 0.8 ng per 1 μL was injected, and the area value was obtained.

特别是，作为低沸点成分的1，1-二氯乙烯、二氯甲烷、反式1，2-二氯乙烯、顺式1，2-二氯乙烯、氯仿的回收率，含有吸附材料的整体吸附件最大，可得到5倍以上的高值，因此可知得到了添加吸附材料的效果(图15)。In particular, the recovery rate of 1,1-dichloroethylene, dichloromethane, trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, and chloroform, which are low-boiling-point components, has a large percentage of the entire adsorption material. The adsorption material was the largest, and a value as high as 5 times or more was obtained, so it can be seen that the effect of adding the adsorption material was obtained ( FIG. 15 ).

<实施例6><Example 6>

作为表面处理之一，在吸附件整体上涂布液相的OV1的比较的图表A comparison graph of OV1, which is a surface treatment that coats the entire adsorbent with a liquid phase

试样成分·浓缩方法与实施例5相同，搅拌时间为60分钟。The sample components and concentration method were the same as in Example 5, and the stirring time was 60 minutes.

C，G，ODS(使整体结构体含有活性炭、石墨，用ODS进行表面处理)C, G, ODS (make the overall structure contain activated carbon and graphite, and use ODS for surface treatment)

C，G，ODS，OV1(在上述吸附件整体上涂布OV1)C, G, ODS, OV1 (coat OV1 on the whole of the above-mentioned adsorbent)

可知，通过使用本申请技术，在间二甲苯、对二甲苯、邻二甲苯等芳香系烃中，可以得到80％左右的回收率，没有相平衡，以完全吸附进行保持(图16)。It can be seen that by using the technology of the present application, in aromatic hydrocarbons such as m-xylene, p-xylene, and o-xylene, a recovery rate of about 80% can be obtained, and there is no phase equilibrium, and it is maintained by complete adsorption (Figure 16).

<实施例7><Example 7>

在自动进样器21的容器22的内部设置整体吸附件23及溶剂24，由于整体吸附件23是内部具有贯通孔25的结构17，因此可以在其容器22内萃取试样，直接用自动进样器向GC注入，所以非常简易、简便。The interior of the container 22 of the autosampler 21 is provided with an integral adsorbent 23 and a solvent 24. Since the integral adsorbent 23 has a structure 17 with a through hole 25 inside, the sample can be extracted in the container 22, and the sample can be directly used for automatic injection. The sampler is injected into the GC, so it is very simple and convenient.

首先，用溶剂24萃取保持在整体吸附件23中的试样。只通过将整体吸附件23浸渍在溶剂24中进行萃取，根据情况有时也照射超声波。用注射器26抽吸萃取好的成分，用GC进行分析(图17，18)。First, the sample held in the monolithic adsorbent 23 is extracted with the solvent 24 . Extraction is performed only by immersing the monolithic adsorbent 23 in the solvent 24, and may also be irradiated with ultrasonic waves in some cases. The extracted components were aspirated with a syringe 26 and analyzed by GC (Fig. 17, 18).

<实施例8><Embodiment 8>

在通常的涂布PDMS的SPME(非整体吸附件)中，试样的保持大多需要时间。特别是在高沸点成分(增塑剂等)的情况下，一般的方法是，还需要加热至试样水温为60～70度左右，使其浸渍，用30分钟～60分钟左右的时间使试样向PDMS保持部保持·吸附。In a typical PDMS-coated SPME (non-monolithic adsorbent), it often takes time to hold a sample. Especially in the case of high-boiling point components (plasticizers, etc.), the general method is to heat the sample to a water temperature of about 60-70 degrees, soak it, and let the sample take about 30 minutes to 60 minutes. The sample is held and adsorbed on the PDMS holding part.

然而，在快速分析中，该时间成为问题。因此对在短时间内使其吸附的方法进行了研究。In fast analysis, however, this time becomes an issue. Therefore, a method of making it adsorb in a short time has been studied.

1)吸附方法11) Adsorption method 1

将本发明的整体吸附件(含活性炭1.5％)32成型为适合容器31的圆锥状的形状，将一端成型为圆锥状，制成其顶端设置开口的容器，收纳在该容器31中，将增塑剂(二丁基羟基甲苯(BHT抗氧化剂)、邻苯二甲酸二丁酯(DBP)、己二酸二酯(DOA))按20ppb的浓度制备5mL的试样(室温)，在外周部用加工了螺纹的固定器具35将整体吸附件32推压固定。用注射器33在整体吸附件32中通入试样，使其保持。所通入的溶液用烧杯34等承接，反复抽吸5次，以使通入后的试样都抽吸、保持。The integral adsorbent (containing 1.5% of activated carbon) 32 of the present invention is molded into a conical shape suitable for the container 31, and one end is molded into a conical shape to make a container with an opening at its top, and it is accommodated in the container 31, increasing the Plasticizers (dibutylhydroxytoluene (BHT antioxidant), dibutyl phthalate (DBP), diester adipate (DOA)) were prepared at a concentration of 20ppb in 5mL samples (at room temperature), and on the periphery The integral adsorption member 32 is pressed and fixed by a threaded fixing device 35 . The sample is passed through the monolithic adsorption member 32 with a syringe 33 to hold it. The passed solution is received by a beaker 34 or the like, and suction is repeated 5 times so that all the passed samples are sucked and held.

保持目标成分后，在整体吸附件32中通入100μL溶剂(二氯甲烷)，与上述同样用烧杯34等承接，反复抽吸进行洗提(图19)。After retaining the target component, 100 μL of solvent (dichloromethane) was poured into the monolithic adsorbent 32 , received in a beaker 34 etc. as above, and repeatedly sucked to carry out elution ( FIG. 19 ).

吸附方法2Adsorption method 2

作为与上述吸附方法1的比较，将5mL的试样注入如图20所示的20mL的容器中，使Disk状(盘状)的整体吸附件浮起，在70度搅拌30分钟使其保持。保持后，取出盘状整体吸附件，用100μL的二氯甲烷用超声波使其洗提。As a comparison with the above-mentioned adsorption method 1, 5 mL of the sample was poured into a 20 mL container as shown in FIG. 20 , the Disk-shaped (disc-shaped) monolithic adsorbent was floated, and stirred at 70°C for 30 minutes to hold it. After holding, the disc-shaped monolithic adsorbent was taken out, and eluted with 100 μL of methylene chloride by ultrasonic waves.

将通过用上述1及2的捕集方法进行的增塑剂的回收用各个面积值①、②表示(图21)。The recovery of the plasticizer by the trapping methods of 1 and 2 above is represented by the respective area values ① and ② ( FIG. 21 ).

相对于如吸附方法2的30分钟的搅拌，在吸附方法1中，通过5次抽吸试样溶液这样的短时间、简易的捕集，可得到如上所述的结果(在增塑剂(BHT·DBP·DOA)中的高回收率)。Compared with the stirring for 30 minutes in the adsorption method 2, in the adsorption method 1, the short-term and simple trapping by aspirating the sample solution 5 times can obtain the above-mentioned results (in plasticizer (BHT · High recovery in DBP · DOA).

另外，通常的固相用5mL左右的溶剂洗提，使其再浓缩成1mL左右，相对于此，在本发明中，将所吸附的目标成分用溶剂洗提时，如本吸附方法1所述，用100μL左右的少量溶剂，而且即使没有再浓缩也能够良好地洗提。可以认为这是抽吸及整体结构的通孔的效果。In addition, the usual solid phase is eluted with about 5 mL of solvent, and then concentrated to about 1 mL. In contrast, in the present invention, when the adsorbed target component is eluted with a solvent, it is as described in this adsorption method 1. , with a small amount of solvent of about 100 μL, and it can be eluted well even without re-concentration. This can be considered an effect of the suction and the through-holes of the monolithic structure.

此外，通过利用抽吸反复向吸附材料通入试样，与现有方法相比，即使是少量的试样溶液也可以有效地吸附。In addition, by repeatedly passing the sample into the adsorbent by suction, even a small amount of sample solution can be efficiently adsorbed compared to the conventional method.

2)使用本发明吸附方法1的含活性炭的效果2) Use the effect of the activated carbon containing adsorption method 1 of the present invention

关于上述利用抽吸的捕集方法中的含活性炭的效果，将水中的TCEP(磷酸三(2-氯乙基)酯)的分析结果表示如下。The results of analysis of TCEP (tris(2-chloroethyl)phosphate) in water are shown below regarding the effect of containing activated carbon in the above-mentioned collection method by suction.

a：将整体硅石表面ODS化之物a: ODS of the overall silica surface

b：将含有3％活性炭的整体硅石表面ODS化之物b: ODS of the surface of monolithic silica containing 3% activated carbon

由面积值得知，通过含有活性炭产生了10倍左右的效果(图22)。From the value of the area, it was found that the effect was about 10 times greater by the inclusion of activated carbon ( FIG. 22 ).

如上述结果所述，可知只用整体硅石ODS保持低沸点成分不能得到满意的结果，含有活性炭等吸附材料依然是有效的方法。As mentioned in the above results, it can be seen that only using monolithic silica ODS to maintain low boiling point components cannot obtain satisfactory results, and the inclusion of adsorbent materials such as activated carbon is still an effective method.

<实施例9><Example 9>

霉臭分析Musty odor analysis

霉臭浓度非常低，用2-MIB、Geosmin通过固相萃取法的定量下限值为0.002μg/L＝0.002ng/mL＝2pg/mL＝2ppt这样的低浓度。The musty odor concentration is very low, and the lower limit of quantification by the solid phase extraction method using 2-MIB and Geosmin is as low as 0.002 μg/L=0.002ng/mL=2pg/mL=2ppt.

另外，由于夹杂成分的影响大、盐析的空白盐、江河水的污染成分等原因，霉臭分析很困难。In addition, due to the great influence of inclusion components, salted-out blank salt, and pollution components of river water, it is difficult to analyze musty odor.

实际上，即使用GCMS、SIM法，有时相同质量数的污染物大多也无法与目标试样成分区分。In fact, even with GCMS and SIM methods, sometimes most of the pollutants with the same mass number cannot be distinguished from the target sample components.

对使用本发明的方法进行说明。The method of using the present invention will be described.

(分析流程)(analysis process)

1.对于样品水，结束老化，添加25％NaCl1. For sample water, end aging, add 25% NaCl

2.将3张盘状的含活性炭整体吸附件放入装有100mL的样品的容器中2. Put 3 disc-shaped integral adsorbents containing activated carbon into the container containing 100mL sample

3.在65℃的带搅拌功能的恒温水箱中搅拌60分钟3. Stir in a constant temperature water tank with stirring function at 65°C for 60 minutes

4.对取出的盘状的含活性炭的整体吸附件用低尘擦拭纸拭去附着的水分。4. Wipe off the attached moisture with a low-dust wiping paper on the disc-shaped integral adsorption piece containing activated carbon that has been taken out.

5.浸渍在1mL的二氯甲烷中，施加超声波用15分钟左右使其洗提。5. Immerse in 1 mL of dichloromethane, and apply ultrasonic waves for about 15 minutes to elute.

6.将1mL的试样用氮气吹扫浓缩至100ul，最终样品量为100μL。6. Concentrate 1 mL of the sample to 100 ul by purging with nitrogen, and the final sample volume is 100 μL.

(实验1回收率试验)(Experiment 1 Recovery Test)

在100mL的矿泉水中添加25％NaCl、添加1μL 2-MIB、Geosmin200ng/mL的浓度，保持在圆盘中，进行浓缩，最终得到100μL的样品试样。当以200pg/100μL注入1μL时，绝对量为2pg/μL。25% NaCl was added to 100 mL of mineral water, 1 μL of 2-MIB, and Geosmin 200 ng/mL were added, kept in a disk, concentrated, and finally 100 μL of a sample sample was obtained. When 1 μL is injected at 200pg/100μL, the absolute amount is 2pg/μL.

为了比较，将200ng/mL的标准试样稀释100倍，对照绝对量(2ng/mL、以1μL计为2pg/mL)，对该试样直接用GCMS、SIM法得到面积值，与上述圆盘所保持的试样的面积值比较，求出回收率。For comparison, the 200ng/mL standard sample was diluted 100 times, compared with the absolute amount (2ng/mL, 2pg/mL in 1 μL), and the area value of the sample was directly obtained by GCMS and SIM methods, and compared with the above disc The area values of the retained samples were compared to obtain the recovery rate.

(实验结果1)(experiment result 1)

回收率，2-MIB：76.95％、Geosmin：72.05％(图23)Recovery rate, 2-MIB: 76.95%, Geosmin: 72.05% (Figure 23)

重复性(n5)2-MIB：6.22％、Geosmin：6.57％Repeatability (n5) 2-MIB: 6.22%, Geosmin: 6.57%

(实验2江河水的污染物的影响的确认)(confirmation of influence of pollutant of experiment 2 river water)

在江河水中有污染物的状况下，2-MIB、Geosmin能否确认的实验The experiment of whether 2-MIB and Geosmin can be confirmed when there are pollutants in the river water

1.添加NaCl以使其浓度为25％，将霉味标准试样添加到100mL江河水中，以使其浓度为2ppt。1. Add NaCl so that the concentration is 25%, and add the musty odor standard sample to 100 mL of river water so that the concentration is 2 ppt.

2.作为比较，在纯水中添加NaCl以使其浓度为25％2. As a comparison, add NaCl to pure water so that its concentration is 25%

3.用二氯甲烷溶剂，按照绝对量与200ppt相同浓度的方式制备的标准试样3. Using dichloromethane solvent, the standard sample prepared in the same way as the absolute amount and 200ppt concentration

研究在实际的江河水中能否确认。在冬季，由于没有产生藻类，因此2-MIB、Geosmin产生的可能性低，在江河水中添加霉臭STD使其浓度为2ppt，用污染物多的江河水，比较2-MIB(图24)、Geosmin能否确认。江河水中的2-MIB难确认，但能够确认。Geosmin(图25)没有问题。Research whether it can be confirmed in actual river water. In winter, because no algae are produced, the possibility of 2-MIB and Geosmin is low. Add mildew STD to the river water to make the concentration 2ppt, and use the river water with many pollutants to compare 2-MIB (Figure 24), Can Geosmin confirm. It is difficult to confirm the 2-MIB in river water, but it can be confirmed. Geosmin (Fig. 25) has no problem.

<实施例10><Example 10>

(室内化学物质的分析)(Analysis of indoor chemical substances)

由于住宅的高度密闭和使用释放化学物质的建筑材料和室内装饰材料等，在新建、改建后的住宅或大楼中，因为由化学物质产生的室内空气污染等而导致的居住者发生各种各样的健康状况不良的情况(所谓病屋综合征)屡有报道。Due to the high airtightness of the residence and the use of building materials and interior decoration materials that release chemical substances, in newly-built or remodeled residences or buildings, various occurrences of occupants due to indoor air pollution caused by chemical substances, etc. Poor health status (so-called sick house syndrome) has been frequently reported.

在厚生劳动省的准则中，提出有各种化学物质，也设定有指标值。因此，需要重复性良好地定量空气中化学物质的技术。In the guidelines of the Ministry of Health, Labor and Welfare, various chemical substances are proposed and index values are set. Therefore, a technique for quantifying chemical substances in the air with good repeatability is required.

(分析方法)(Analytical method)

挥发性有机化合物用固相吸附/溶剂萃取法、固相吸附/加热脱附法、容器采集法三种方法中的某种方法采集，用气相色谱-质谱分析法(GC-MS)进行分析。Volatile organic compounds were collected by one of the three methods of solid phase adsorption/solvent extraction, solid phase adsorption/heating desorption, and container collection, and analyzed by gas chromatography-mass spectrometry (GC-MS).

抽吸方式(主动法)一般使用灵敏度最高的加热脱附法，扩散方式(被动法)一般使用利用加热脱附法的溶剂萃取法(二硫化碳)。The suction method (active method) generally uses the most sensitive heating desorption method, and the diffusion method (passive method) generally uses the solvent extraction method (carbon disulfide) using the heating desorption method.

以下记录本实验流程。The experimental procedure is recorded below.

1.采样1. Sampling

抽吸流量：1.0L/分钟Suction flow: 1.0L/min

2.试样导入2. Sample introduction

PTV：40℃、16℃/秒、280℃(5分钟)PTV: 40°C, 16°C/sec, 280°C (5 minutes)

3.色谱柱3. Column

InertCap 5MS、0.25mmIDx 30M、df＝0.25μmInertCap 5MS, 0.25mmIDx 30M, df=0.25μm

4.烘箱温度4. Oven temperature

40℃(3分钟)、20℃/分钟280℃(5分钟)40°C (3 minutes), 20°C/min 280°C (5 minutes)

在现有的利用固相吸附/加热脱附的毛细管GC试样导入法中，利用专用的加热脱附装置实施试样导入，进而，对于甲苯、二甲苯异构体(邻位体、间位体、对位体)，为了得到高分离，需要使用液氮的冷阱，因此，相对于1分析有花费成本、时间这样的缺点。In the existing capillary GC sample introduction method utilizing solid phase adsorption/heating desorption, the sample is introduced using a dedicated heating desorption device, and further, for toluene and xylene isomers (ortho, meta Body, para body), in order to obtain a high separation, it is necessary to use a cold trap of liquid nitrogen, therefore, compared with the 1 analysis, there are disadvantages such as cost and time.

相对于此，在利用整体吸附件的分析中，利用PTV注入口，即使不施用冷阱，甲苯、二甲苯异构体也可充分得到分离。这种方法与现有方法相比，分析成本降低，分析时间缩短，而且还可提高分析精度(图26，27)。On the other hand, in the analysis using the monolithic adsorbent, the PTV injection port can sufficiently separate toluene and xylene isomers without using a cold trap. Compared with the existing methods, this method reduces the analysis cost, shortens the analysis time, and improves the analysis accuracy (Fig. 26, 27).

<实施例11><Example 11>

利用被动取样的整体吸附件的效果。The effect of monolithic sorbents utilizing passive sampling.

将袋盖在栀子上，其中使整体吸附件、SPME暴露，进行被动取样(暴露3小时)。整体吸附件暴露后，用1mL二氯甲烷进行溶剂萃取，浓缩至100μL的容量，向GCMS注入1μL。SPME暴露后，直接向GCMS注入。Passive sampling was performed by placing the bag over the gardenia with the monolithic sorbent, SPME exposed (3 hours exposure). After the monolithic adsorbent was exposed, solvent extraction was performed with 1 mL of dichloromethane, concentrated to a volume of 100 μL, and 1 μL was injected into the GCMS. After SPME exposure, inject directly into GCMS.

根据利用本发明的整体吸附件的取样，能够良好地确认吲哚(图36中①)(图36)。According to sampling using the monolithic adsorbent of the present invention, indole can be confirmed well (① in FIG. 36 ) ( FIG. 36 ).

可知因整体吸附件的捕集能力大，故即使用溶剂萃取稀释100倍，得到的灵敏度也不逊色于全量注入的加热脱附(SPME)。It can be seen that due to the large collection capacity of the monolithic adsorbent, even if it is diluted 100 times by solvent extraction, the sensitivity obtained is not inferior to that of the full injection of thermal desorption (SPME).

<实施例12><Example 12>

通过向整体吸附件通入水，确认能否充分萃取试样的实验An experiment to confirm whether the sample can be sufficiently extracted by passing water through the monolithic adsorbent

1.试样制备1. Specimen Preparation

(1)试样水溶液(1) Sample aqueous solution

制备包含10ng/L的2-甲基异莰醇(2-MIB)和Geosmin的水溶液。An aqueous solution containing 10 ng/L of 2-methylisoborneol (2-MIB) and Geosmin was prepared.

(2)回收率确认用试样(2) Sample for confirmation of recovery rate

制备包含1ng/μL的2-甲基异莰醇(2-MIB)和Geosmin的甲醇溶液。A methanol solution containing 1 ng/μL of 2-methylisoborneol (2-MIB) and Geosmin was prepared.

2.萃取方法2. Extraction method

用注射筒采样100mL试样水溶液，手动直接向作为本发明整体吸附件的硅石整体型固相萃取剂通入水。Use a syringe to sample 100mL sample aqueous solution, and manually pass water directly into the silica monolithic solid-phase extractant as the monolithic adsorbent of the present invention.

3.装置3. Device

(1)GC.MS：TraceGC，PolarisQ(赛默飞世尔科技公司)(1) GC.MS: TraceGC, PolarisQ (Thermo Fisher Scientific Corporation)

离子化法：EI，离子源温度：200℃，界面温度：280℃，扫描范围(m/z)：50～450Ionization method: EI, ion source temperature: 200°C, interface temperature: 280°C, scan range (m/z): 50～450

(2)试样导入法：PTV不分流进样法(ATAS GL OPTIC3)(2) Sample introduction method: PTV splitless sampling method (ATAS GL OPTIC3)

注入口温度：初期温度40℃、升温速度16℃/秒，最终温度280℃(5分钟)Injection port temperature: initial temperature 40°C, heating rate 16°C/sec, final temperature 280°C (5 minutes)

(3)分析柱：InertCap 5MS，0.25mmIDx30M，df＝0.25μm(GLS公司制)(3) Analytical column: InertCap 5MS, 0.25mmIDx30M, df=0.25μm (manufactured by GLS Corporation)

(4)GC烘箱温度程序：40℃(3分钟)-20℃/分钟-280℃(10分钟)(4) GC oven temperature program: 40°C (3 minutes) -20°C/min -280°C (10 minutes)

4.结果与研究4. Results and Research

图30，31和图33，34的下方所示的质谱(图32、图35)测出基峰m/z 95、分子离子峰值M+168、可以确认为2-MIB，另外，测出基峰m/z112、m+182、可以确认为Geosmin。The mass spectrum (Fig. 32, Fig. 35) shown below Fig. 30, 31 and Fig. 33, 34 shows the base peak m/z 95, the molecular ion peak M + 168, which can be confirmed as 2-MIB. In addition, the base peak Peak m/z 112, m + 182, can be confirmed as Geosmin.

图30、图33是利用硅石整体型固相萃取材料通入试样水溶液100mL，用PTV不分流注入法全量导入吸附成分的色谱图，图31、图34是注入1μL回收率确认用试样(1ng/μL的2-MIB和Geosmin)的色谱图。图32、图35分别是2-MIB、Geosmin的色谱图。Fig. 30 and Fig. 33 are the chromatograms of introducing 100mL of the sample aqueous solution into 100mL of the sample aqueous solution by using the silica monolithic solid-phase extraction material, and using the PTV splitless injection method to introduce the full amount of the adsorbed components. Fig. 31 and Fig. 34 are injected into 1 μL of the recovery confirmation sample ( Chromatogram of 1ng/μL of 2-MIB and Geosmin). Figure 32 and Figure 35 are the chromatograms of 2-MIB and Geosmin, respectively.

在图30和31、图33和34中，填充的上下的色谱峰面积值显示出良好的一致。这说明本发明整体吸附件对霉臭成分具有高吸附性。In Figures 30 and 31, and Figures 33 and 34, the chromatographic peak area values above and below the fill show good agreement. This shows that the integral adsorbent of the present invention has high adsorbability to musty odor components.

另外，因为峰值形状也良好，所以也说明作为吸附在本发明整体吸附件上的霉臭成分的加热脱附试样导入方法，可使用PTV不分流注入方法。In addition, since the peak shape is also good, it is also explained that the PTV splitless injection method can be used as the heating desorption sample introduction method of the musty odor component adsorbed on the monolithic adsorbent of the present invention.

<实施例13><Example 13>

与SBSE的比较。Comparison with SBSE.

在本发明整体吸附件和20mL的15％NaCl水溶液中，添加相当于5ng的下述的标准试样，用整体吸附件及PDMS基质的SBSE进行捕集。在恒温振荡水箱中在60度、以90rpm搅拌30分钟。To the monolithic adsorbent of the present invention and 20 mL of 15% NaCl aqueous solution, 5 ng of the following standard sample was added, and the monolithic adsorbent and PDMS-based SBSE were used for capture. Stir in a constant temperature shaking water tank at 60 degrees and 90 rpm for 30 minutes.

整体吸附件用二氯甲烷萃取200μL、SBSE用乙腈萃取200μL，进行测定。The monolithic adsorbent was extracted with 200 μL of dichloromethane, and the SBSE was extracted with 200 μL of acetonitrile for measurement.

使试样的水-辛醇分配系数(LogP)为横轴，表示绝对回收率(图38)。The water-octanol partition coefficient (LogP) of the sample is plotted on the abscissa to represent the absolute recovery ( FIG. 38 ).

LogP值低的试样为亲水性，从水中回收会非常困难，但即使是这样的试样，整体吸附件也可得到整体比SBSE高的回收率。即使水-辛醇分配系数为1以下(甲基吡嗪、2，6-二甲基吡嗪)，也可得到19％以上的回收率。Samples with a low LogP value are hydrophilic, and recovery from water is very difficult, but even for such samples, the monolithic adsorbent can obtain a recovery rate higher than that of SBSE as a whole. Even when the water-octanol partition coefficient is 1 or less (methylpyrazine, 2,6-dimethylpyrazine), a recovery rate of 19% or more can be obtained.

(水-辛醇分配系数：试样)(Water-octanol partition coefficient: sample)

0.21：甲基吡嗪0.21: methylpyrazine

0.54；2，6-二甲基吡嗪0.54; 2,6-dimethylpyrazine

1.39：香豆素1.39: Coumarin

2.14：吲哚2.14: Indole

2.74：桉油酚2.74: Eucalyptol

2.85：橙色水晶(Orange clystal)2.85: Orange clystal

2.97：芳樟醇2.97: Linalool

3.05：辛酸3.05: Caprylic acid

4.20：柠檬油精4.20: Limonene

<实施例14><Example 14>

关于吸附时间和回收率的关系(气体试样)Relationship between adsorption time and recovery rate (gas sample)

在盖严的容器(容量40mL)中添加相当于气中密度125ppb的标准气体试样(与沸点一起记录于图中)，用整体吸附件(盘状)进行吸附(60℃)。Add a standard gas sample corresponding to a density of 125ppb in air (recorded in the figure together with the boiling point) in a tightly-capped container (capacity 40mL), and perform adsorption (60°C) with a monolithic adsorbent (disk-shaped).

将吸附率与保持时间的关系示于图39。为了得到可靠的吸附，需要30～60分钟左右的吸附时间，但随着试样的不同，即使少于该时间也可充分回收。The relationship between the adsorption rate and the retention time is shown in FIG. 39 . In order to obtain reliable adsorption, an adsorption time of about 30 to 60 minutes is required, but depending on the sample, sufficient recovery can be achieved even if it is shorter than this time.

利用PDMS的液相从吸附、液体中萃取因相平衡而需要较长时间，但由于整体吸附件利用在键合在二氧化硅骨架表面部的相邻的ODS基的缝隙间通入试样的吸附发挥了较大的作用，所以可容易地缩短吸附时间。The adsorption and extraction of the liquid phase using PDMS takes a long time due to phase equilibrium, but since the monolithic adsorbent uses the gap between the adjacent ODS groups bonded to the surface of the silica skeleton to pass through the sample Adsorption plays a large role, so the adsorption time can be easily shortened.

<实施例15><Example 15>

关于温度和吸附率的关系(气体试样)。The relationship between temperature and adsorption rate (gas sample).

比较在上述实施例14中吸附时的温度30℃、60℃的吸附率(吸附时间30分钟)。The adsorption rate (adsorption time: 30 minutes) at the temperature of 30° C. and 60° C. during the adsorption in the above-mentioned Example 14 was compared.

因为气体的扩散系数依存于温度，所以可通过加温缩短吸附时间。将使用试样活性低的芳樟醇和橙色水晶的实验结果示于图40。Since the diffusion coefficient of gas depends on temperature, the adsorption time can be shortened by heating. The experimental results using linalool and orange crystals with low sample activity are shown in FIG. 40 .

<实施例16><Example 16>

关于盐析About salting out

将25μL标准试样(200μg/mL)添加在20mL的15％NaCl水溶液中，用1张盘状整体吸附件吸附。在恒温振荡水箱中在60℃、以90rpm搅拌30分钟。其结果，如图41所示，利用盐析效果使整体吸附率增加了。25 µL of a standard sample (200 µg/mL) was added to 20 mL of a 15% NaCl aqueous solution, and adsorbed by one disc-shaped monolithic adsorbent. Stir in a constant temperature shaking water tank at 60° C. and 90 rpm for 30 minutes. As a result, as shown in Fig. 41, the overall adsorption rate was increased by the salting-out effect.

<实施例17><Example 17>

关于吸附时间和吸附率的关系(液体试样)。About the relationship between adsorption time and adsorption rate (liquid sample).

将25μL标准试样(200μg/mL)添加在20mL的15％NaCl水溶液中，用1张盘状整体吸附件吸附。在恒温振荡水箱中在60℃、以90rpm搅拌30分钟。顶空分析也在60℃加温静置。25 µL of a standard sample (200 µg/mL) was added to 20 mL of a 15% NaCl aqueous solution, and adsorbed by one disc-shaped monolithic adsorbent. Stir in a constant temperature shaking water tank at 60° C. and 90 rpm for 30 minutes. Headspace analysis was also heated at 60°C and left to stand.

在顶空分析法的情况下，为了利用扩散作用达到平衡而需要时间。在(图42)搅拌的情况下，用30分钟左右达到平衡(图43)。In the case of headspace analysis, it takes time to reach equilibrium by diffusion. With stirring (FIG. 42), it takes about 30 minutes to reach equilibrium (FIG. 43).

但是，在酸性试样辛酸的情况下需要60分钟左右。However, in the case of the acidic sample caprylic acid, it takes about 60 minutes.

<实施例18><Example 18>

关于pH调节和回收率的关系(液体试样)。Regarding the relationship between pH adjustment and recovery (liquid samples).

将25μL标准试样(200ug/mL)添加在20mL的15％NaCl水溶液(用1M-磷酸调节pH为2)中，用一张盘状整体吸附件吸附。在恒温振荡水箱中在60℃、以90rpm搅拌30分钟。顶空分析(HS)也在60℃加温，静置30分钟。Add 25 μL of standard sample (200 ug/mL) to 20 mL of 15% NaCl aqueous solution (adjust pH to 2 with 1M-phosphoric acid), and adsorb it with a disc-shaped monolithic adsorbent. Stir in a constant temperature shaking water tank at 60° C. and 90 rpm for 30 minutes. Headspace analysis (HS) was also heated at 60°C and allowed to stand for 30 minutes.

将有无调节试样(辛酸)的pH的差别、HS及搅拌的结果示于图44。Fig. 44 shows the difference between the pH of the sample (octanoic acid) and the results of HS and stirring.

a：HSa: HS

b：调节了pH的HSb: pH-adjusted HS

c：搅拌c: stir

d：调节了pH的搅拌d: Stirring with adjusted pH

可知通过控制水试样的pH，吸附率提高，盐析对水试样的吸附有效，提高进一步控制试样的pH，可进一步提高吸附率。It can be seen that by controlling the pH of the water sample, the adsorption rate is improved, and salting out is effective for the adsorption of the water sample, and further controlling the pH of the sample can further increase the adsorption rate.

对吸附·萃取效率而言，在液体试样的情况下，大大依存于试样的特性或基质的影响等，因此，为了提高吸附率，同时使用盐析·pH调节等手段是有效的。In the case of liquid samples, the adsorption and extraction efficiency greatly depends on the characteristics of the sample and the influence of the matrix. Therefore, in order to improve the adsorption rate, it is effective to use measures such as salting out and pH adjustment at the same time.

<实施例19><Example 19>

关于超声波照射和吸附率的关系About the relationship between ultrasonic irradiation and adsorption rate

在盖严的容器(容量40mL)中，添加相当于气中密度125ppb的标准试样，用盘状整体吸附件吸附(60℃)。改变溶剂萃取时的超声波处理时间，进行测定。Add a standard sample corresponding to a density of 125ppb in air into a tightly capped container (capacity 40mL), and adsorb it with a disc-shaped monolithic adsorbent (60°C). Measurements were performed while changing the ultrasonic treatment time during solvent extraction.

使用500μL二氯甲烷，将用超声波照射的不同时间的吸附率的变化示于图45。可知用1分钟左右的超声波照射可得到充分的吸附率。Fig. 45 shows the change in the adsorption rate at different times of ultrasonic irradiation using 500 µL of dichloromethane. It can be seen that a sufficient adsorption rate can be obtained by ultrasonic irradiation for about 1 minute.

<实施例20><Example 20>

关于萃取用溶剂About extraction solvents

在盖严的容器(容量40mL)中，添加相当于气中密度100ppb的标准试样，用盘状整体吸附件吸附(60℃)，其后用500μL溶剂萃取。Add a standard sample corresponding to a density of 100 ppb in air into a tightly capped container (capacity 40 mL), adsorb it with a disc-shaped monolithic adsorbent (at 60° C.), and then extract it with 500 μL of solvent.

萃取时使用的溶剂根据目标试样进行选择。可使用普通的丙酮(图46中①)、二乙基醚(图46中②)、C6(图46中③)、甲醇(图46中④)、二氯甲烷(图46中⑤)、乙醇、己烷(图46中⑤)等。在本实验中，二氯甲烷可平衡良好地萃取。The solvent used for extraction is selected according to the target sample. Ordinary acetone (① in Figure 46), diethyl ether (② in Figure 46), C6 (③ in Figure 46), methanol (④ in Figure 46), dichloromethane (⑤ in Figure 46), ethanol can be used , hexane (⑤ in Figure 46), etc. In this experiment, dichloromethane was well-balanced for extraction.

a：柠檬油精、b：桉油酚、c：β-芳樟醇、d：甲基吡嗪、e：2，6-二甲基吡嗪、f：吲哚、g：樟脑、h：辛酸、i：香豆素、j：橙色水晶(图46)a: limonene, b: eucalyptol, c: β-linalool, d: methylpyrazine, e: 2,6-dimethylpyrazine, f: indole, g: camphor, h: Caprylic acid, i: coumarin, j: orange crystal (Figure 46)

<实施例21><Example 21>

对以除去基质成分43等为目的的整体结构体(整体预过滤器41)而言，使可除去、保持对象成分的试剂在整体结构体表面反应或使其包含在整体自身中。主要的物质可举出离子交换相(SAX、SCX等)、特殊结合相(PBA等)、极性相(S1、FL等)、非极性相(SDB、C18等)、顺相吸附(活性炭、石墨碳离子交换体系、Cl、CN)。In the monolithic structure (monolithic prefilter 41 ) for the purpose of removing the matrix component 43 and the like, a reagent capable of removing and retaining the target component is reacted on the surface of the monolithic body or contained in the monolith itself. The main substances include ion exchange phases (SAX, SCX, etc.), special binding phases (PBA, etc.), polar phases (S1, FL, etc.), non-polar phases (SDB, C18, etc.), along-phase adsorption (activated carbon, etc.) , graphite carbon ion exchange system, Cl, CN).

这些当然也可以同样使整体吸附件42含有、修饰。使其选择性更高地保持时，使例如整体预过滤器41含有活性炭，不进行ODS处理使其处于有亲水性的状态，用内部的整体吸附件42可以选择性地保持(图28)。Of course, these can also be included and modified by the integral adsorption member 42 in the same way. To maintain it more selectively, for example, the integrated pre-filter 41 contains activated carbon, and is not subjected to ODS treatment to make it in a hydrophilic state, and can be selectively maintained by the internal integrated adsorption member 42 ( FIG. 28 ).

<实施例22><Example 22>

对于有机磷系农药，通过在整体预过滤器41中不进行ODS处理使其处于有亲水性的状态，使内部的整体吸附件42有疏水性，该农药的水分被外部的预过滤器吸收，可以在内部吸附该农药的疏水性成分(马拉硫磷、杀螟硫磷、MEP、三氯磷酸酯、DDVP、敌敌畏、甲噻硫磷、乙酰甲胺磷、异恶唑磷等44)For organophosphorus pesticides, by not performing ODS treatment in the integral pre-filter 41 to make it hydrophilic, the internal integral adsorption member 42 is made hydrophobic, and the moisture of the pesticide is absorbed by the external pre-filter , which can adsorb the hydrophobic components of the pesticide (malathion, fenitrothion, MEP, trichlorophosphate, DDVP, dichlorvos, methion, acephate, isoxazophos, etc. 44)

对于由有机磷系农药引起的中毒，在确定治疗原则上需要迅速使用解毒剂PAM。确立迅速分析呕吐物或其他活体试样中的有机磷系农药的方法十分重要，通过使用本发明，缩短吸附、萃取时间对其效果相当有用。For poisoning caused by organophosphorus pesticides, the antidote PAM needs to be used promptly in principle of definite treatment. It is very important to establish a method for rapid analysis of organophosphorus pesticides in vomitus or other living samples, and shortening the adsorption and extraction time is very useful for its effect by using the present invention.

另外，因为有机磷系农药有挥发性，所以在溶剂萃取的目标成分的浓缩中要谨慎，而用如本发明的封闭系统进行目标成分的吸附，可直接用GC或LC进行分析，解决了此问题。In addition, because organophosphorus pesticides are volatile, care should be taken in the concentration of the target components of solvent extraction, and the adsorption of the target components with the closed system of the present invention can be directly analyzed by GC or LC, which solves this problem. question.

<实施例23><Example 23>

在作为判断亲水性、疏水性的指标的水-辛醇分配系数(LogP)的数值低为1以下左右的试样(亲水性)中，难以从水中萃取。In a sample (hydrophilicity) whose water-octanol partition coefficient (LogP), which is an index for judging hydrophilicity and hydrophobicity, is as low as about 1 or less, extraction from water is difficult.

例如，醋酸的LogP为0.09，作为萃取法，可举出使溶液为酸性或盐析等手段，但繁琐且困难。For example, the LogP of acetic acid is 0.09. As the extraction method, there are methods such as making the solution acidic or salting out, but these are cumbersome and difficult.

这样，相对于水中的脂肪酸(特别是醋酸、丙酸、丁酸)等亲水性质的整体吸附件，由于其表面为疏水性而不沾水分，因此，硅石骨架内部的孔(介孔)不参与，造成吸附困难。In this way, compared to the monolithic adsorbents with hydrophilic properties such as fatty acids in water (especially acetic acid, propionic acid, butyric acid), the surface is hydrophobic and does not stick to water, so the pores (mesopores) inside the silica skeleton are not Participation makes adsorption difficult.

因此，通过使整体吸附件表面为亲水性，试样和吸附件的亲合性变得良好，容易吸附目标成分。为了使其为亲水性，对吸附件表面进行酸处理或使用具有二醇基的烷氧基硅烷等反应试剂。Therefore, by making the surface of the monolithic adsorbent hydrophilic, the affinity between the sample and the adsorbent becomes good, and the target component is easily adsorbed. In order to make it hydrophilic, acid treatment is performed on the surface of the adsorbent, or a reactive agent such as alkoxysilane having a glycol group is used.

在本实施例中，为了吸附水中的脂肪酸(下述C2～C7)，用反应试剂使吸附件为亲水性，使所述吸附件浸渍在试样溶液中。将所述整体吸附件加热到60℃，吹入吹扫气体除去水分，其后用二乙基醚实施溶剂萃取。(图47)In this example, in order to adsorb fatty acids (C2 to C7 below) in water, the adsorbent was made hydrophilic with a reagent, and the adsorbent was immersed in a sample solution. The monolithic adsorbent was heated to 60° C., and a purge gas was blown to remove moisture, after which solvent extraction was performed with diethyl ether. (Figure 47)

C2：乙酸C2: acetic acid

C3：丙酸C3: propionic acid

C4：丁酸C4: butyric acid

C5：戊酸C5: Valeric acid

C6：己酸C6: caproic acid

C7：庚酸C7: Heptanoic acid

将上述各试样的用亲水性表面(a)/疏水性(b)的吸附件的比较示于图48。另外，将以水-辛醇分配系数(logP)为横轴的情况的比较示于图49。由根据这些的结果可知，对于水-辛醇分配系数低的亲水性试样有用。Fig. 48 shows a comparison of the adsorbents using the hydrophilic surface (a)/hydrophobic (b) of the above-mentioned samples. In addition, the comparison of the case where the water-octanol partition coefficient (logP) is taken as the abscissa is shown in FIG. 49 . From these results, it can be seen that it is useful for a hydrophilic sample having a low water-octanol partition coefficient.

产业上的可利用性Industrial availability

根据本发明，尽管是与SPME或SBSE相同体积的固定相，但是通过制成整体结构体，固定相自身的厚度变薄，表面积增大，其结果，可在较短时间内捕集(达到平衡状态)、萃取(脱附)。According to the present invention, although it is a stationary phase with the same volume as SPME or SBSE, by making it into a monolithic structure, the thickness of the stationary phase itself becomes thinner and the surface area increases. state), extraction (desorption).

除此此外，具有暴露在整体结构体的表面部的吸附材料的效果和在整体结构体表面部ODS(十八烷基硅烷)、SDB(苯乙烯二乙烯基苯共聚物)或二醇等疏水性乃至亲水性化合物进行反应的效果的协同效果，根据情况进而实施将树脂PDMS(聚二甲基硅氧烷)、PEG(聚乙二醇)等涂布在整体吸附件整体上等的表面处理，由此能够增强吸附能力。In addition, it has the effect of the adsorption material exposed on the surface of the monolithic body and the hydrophobicity of ODS (octadecylsilane), SDB (styrene divinylbenzene copolymer) or diol on the surface of the monolithic body. The synergistic effect of the effect of the reaction of the chemical and even the hydrophilic compound, and depending on the situation, the resin PDMS (polydimethylsiloxane), PEG (polyethylene glycol), etc. are coated on the surface of the whole adsorption material, etc. treatment, thereby enhancing the adsorption capacity.

另外，由于是整体结构体，因此，因具有连续的孔结构和具有许多介孔，故表面积增大，目标溶液中的试样成分与吸附材料及ODS等烷氧基硅烷系试样的接触面积大，所以增加了吸附能力。In addition, because it is a monolithic structure, it has a continuous pore structure and many mesopores, so the surface area increases, and the contact area between the sample components in the target solution and the adsorption material and alkoxysilane-based samples such as ODS Large, so the adsorption capacity is increased.

利用如上所述的表面积、吸附材料、疏水性乃至亲水性化合物、试剂等的协同效果，可进一步改善对试样的吸附。Adsorption to the sample can be further improved by utilizing the synergistic effect of surface area, adsorption material, hydrophobic or even hydrophilic compound, reagent, etc. as described above.

洗提PDMS等所保持的试样成分时，用于通过相平衡进行解吸的表面积少的现有方法不理想。相对于现有方法，本方法因为整体吸附件表面积大，所以洗提时与脱附气体或溶剂的接触面积大，可解吸非常少量的气体或溶剂的溶质成分。When eluting sample components held by PDMS or the like, the conventional method, which has a small surface area for desorption by phase equilibrium, is not ideal. Compared with the existing method, this method has a large surface area of the overall adsorbent, so the contact area with the desorbed gas or solvent is large during elution, and a very small amount of solute components of the gas or solvent can be desorbed.

另外，表面积大和吸附能力改善意味着整体吸附件本身的小型化，特别是在GC、LC分析中具有重要的意义。例如，如果在现行的GC自动进样器样品瓶中收纳本发明吸附材料，则可以用少量的溶剂解吸，直接用自动进样器进行自动分析，可非常简易、廉价地进行浓缩分析。In addition, the large surface area and improved adsorption capacity mean the miniaturization of the overall adsorbent itself, which is of great significance especially in GC and LC analysis. For example, if the adsorption material of the present invention is stored in the sample bottle of the current GC autosampler, it can be desorbed with a small amount of solvent, and the autosampler can be directly used for automatic analysis, and concentrated analysis can be performed very simply and cheaply.

在对环境水等进行浓缩分析的情况下，有时混杂在环境水中的基质成分对目标试样有干扰。现行的方法是通过预先过滤等除去干扰成分后进行浓缩，但该工序大多费时、繁琐。In the case of concentrated analysis of environmental water or the like, matrix components mixed in the environmental water may interfere with the target sample. The current method is to remove interfering components by pre-filtration and then concentrate, but this process is often time-consuming and cumbersome.

然而，本方法可一次性完成除去其干扰成分和仅对目标试样选择性吸附、保持。在盖部的整体结构体中除去基质，进而在内部吸附整体材料中只选择性吸附目标试样。However, this method can remove its interfering components and selectively adsorb and retain only the target sample at one time. The matrix is removed from the monolithic structure of the cover, and only the target sample is selectively adsorbed in the interior adsorption monolith.

另外，将盘状的基质除去机构50(相当于上述盖部)、整体吸附件51可粘贴地设置在容器内，也可得到同样效果(图29)。In addition, the same effect can also be obtained by adhering the disk-shaped matrix removing mechanism 50 (corresponding to the above-mentioned cover part) and the integral adsorption member 51 in the container (FIG. 29).

通过向本发明整体吸附件正确地通液试样溶液，可得到吸附量及吸附时间、吸附的简易性(数次抽吸)更加提高的效果。通过将用于萃取目标成分的溶剂也同样通液，用少量溶剂即可产生回收效果，结果可在高浓度下进行分析。By accurately passing the sample solution through the monolithic adsorbent of the present invention, the effect of further improving the adsorption capacity, adsorption time, and ease of adsorption (several times of suction) can be obtained. By passing the solvent used to extract the target component in the same way, the recovery effect can be produced with a small amount of solvent, and as a result, analysis can be performed at a high concentration.

另外，在热萃取中，产生缩短萃取时间的效果。利用这些效果，还产生如下效果：可得到在色谱中的尖锐的峰，目标成分的热负荷受到抑制，可不在受基质存在的影响的条件下得到充分的吸附量。In addition, in hot extraction, there is an effect of shortening the extraction time. Utilizing these effects also produces the effect that a sharp peak in the chromatogram can be obtained, the heat load of the target component can be suppressed, and a sufficient amount of adsorption can be obtained without being affected by the presence of a matrix.

另外，利用本发明的整体吸附件，可将用该整体吸附件吸附的试样用溶剂、热进行洗提并直接导入分析装置，可省去如现有方法那样在容器中洗提试样再送到注入口的麻烦，可用少量的溶剂洗提，另外，也有加热洗提容易的效果。In addition, using the integral adsorbent of the present invention, the sample adsorbed by the integral adsorbent can be eluted with solvent and heat and directly introduced into the analysis device, which can save the need to elute the sample in the container as in the existing method and then send it. It can be eluted with a small amount of solvent without trouble to the injection port, and also has the effect of easy heating and elution.

在本发明装置、方法中，即使大量地流过低浓度的试样的情况下，目标试样也不会从吸附材料中流出(穿透、突破)，能够可靠地保持试样。结构体没有破损，能够可靠地保持试样。In the apparatus and method of the present invention, even when a large amount of low-concentration sample flows through, the target sample does not flow out (breakthrough, break through) from the adsorbent, and the sample can be reliably held. The structure was not damaged, and the sample could be reliably held.

在本发明中，对于试样而言，液体或气体均可使用，作为液体试样，能够应用于抽吸、浸渍、溶液中的搅拌、顶空分析、动态顶空分析、搅拌器等，作为气体试样，可以应用于主动采样器、被动采样器等。In the present invention, for the sample, either liquid or gas can be used, and as a liquid sample, it can be applied to suction, immersion, stirring in a solution, headspace analysis, dynamic headspace analysis, stirrer, etc., as Gas samples can be applied to active samplers, passive samplers, etc.

Claims (20)

1.用于向分析装置导入试样的整体吸附件，其特征在于，使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部，同时将化学物质涂布或化学结合在该整体结构体上；1. An integral adsorbent for introducing a sample into an analysis device, characterized in that the integral structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the integral structure, and chemical substances are coated or chemically bonded at the same time on the monolithic structure; 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 2.如权利要求1所述的用于向分析装置导入试样的整体吸附件，其特征在于，将具有疏水性或亲水性的化学物质化学结合在所述整体结构体表面。2. The monolithic adsorbent for introducing a sample into an analysis device according to claim 1, wherein a hydrophobic or hydrophilic chemical substance is chemically bonded to the surface of the monolithic structure. 3.如权利要求1所述的用于向分析装置导入试样的整体吸附件，其特征在于，使树脂涂布或化学结合在所述整体结构体表面。3. The monolithic adsorbent for introducing a sample into an analysis device according to claim 1, wherein a resin is coated or chemically bonded to the surface of the monolithic structure. 4.如权利要求2所述的用于向分析装置导入试样的整体吸附件，其特征在于，进而使树脂涂布或化学结合在所述利用具有疏水性或亲水性的化学物质进行了表面处理的所述整体结构体上。4. The monolithic adsorbent for introducing a sample into an analysis device according to claim 2, wherein resin coating or chemical bonding is carried out in said hydrophobic or hydrophilic chemical substance. surface treatment on the integral structure. 5.如权利要求2或4所述的用于向分析装置导入试样的整体吸附件，其特征在于，所述具有疏水性的化学物质含有具有选自十八烷基、甲基、乙基、辛基、环己基、乙烯基、苯基中的官能团的一种或多种的化合物。5. The integral adsorbent for introducing a sample into an analysis device as claimed in claim 2 or 4, wherein the hydrophobic chemical substance contains an octadecyl group, a methyl group, an ethyl group , octyl, cyclohexyl, vinyl, phenyl functional groups in one or more compounds. 6.如权利要求2或4所述的用于向分析装置导入试样的整体吸附件，其特征在于，所述具有亲水性的化学物质是具有选自二醇基、氰丙基、乙基羧基、磺酸基丙基、丙基苯磺酸基、氨基丙基、乙二胺-N-丙基、三甲基氨基丙基、聚酰胺基中的官能团的一种或多种的化合物。6. The integral adsorbent for introducing a sample into an analysis device as claimed in claim 2 or 4, wherein the hydrophilic chemical substance is selected from glycol, cyanopropyl, ethyl A compound of one or more functional groups in carboxyl group, sulfopropyl group, propylbenzenesulfonate group, aminopropyl group, ethylenediamine-N-propyl group, trimethylaminopropyl group, polyamide group . 7.如权利要求3或4所述的用于向分析装置导入试样的整体吸附件，其特征在于，所述树脂含有选自具有硅氧烷骨架的树脂、具有亲水性的树脂、具有疏水性的树脂中的一种或多种的混合物。7. The integral adsorbent for introducing a sample into an analysis device according to claim 3 or 4, wherein the resin contains a resin selected from a resin having a siloxane skeleton, a hydrophilic resin, a resin having One or more mixtures of hydrophobic resins. 8.如权利要求7所述的用于向分析装置导入试样的整体吸附件，其特征在于，所述具有硅氧烷骨架的树脂含有选自聚二甲基硅氧烷、硅亚苯基硅氧烷、二苯基硅氧烷、氰丙基苯基硅氧烷、氰丙基硅氧烷中的一种或多种的混合物。8. The integral adsorbent for introducing a sample into an analysis device as claimed in claim 7, wherein the resin having a siloxane skeleton contains a compound selected from polydimethylsiloxane, silicon phenylene One or more mixtures of siloxane, diphenylsiloxane, cyanopropylphenylsiloxane, and cyanopropylsiloxane. 9.如权利要求7所述的用于向分析装置导入试样的整体吸附件，其特征在于，所述具有亲水性的树脂含有选自聚乙二醇、聚对苯二甲酸乙二醇酯、聚丙烯、二醇、碳蜡、聚丙烯酸、多元胺中的一种或多种的混合物。9. The integral adsorbent for introducing a sample into an analysis device as claimed in claim 7, wherein the hydrophilic resin contains a compound selected from the group consisting of polyethylene glycol, polyethylene terephthalate One or more mixtures of ester, polypropylene, glycol, carbon wax, polyacrylic acid and polyamine. 10.如权利要求7所述的用于向分析装置导入试样的整体吸附件，其特征在于，所述具有疏水性的树脂含有选自二乙烯基苯共聚物、苯乙烯共聚物、丙烯共聚物中的一种或多种的混合物。10. The integral adsorbent for introducing a sample into an analysis device according to claim 7, wherein the hydrophobic resin contains a compound selected from divinylbenzene copolymer, styrene copolymer, propylene copolymer A mixture of one or more of them. 11.试样吸附方法，其特征在于，在收纳有液体或气体试样的容器内，收纳用于向分析装置导入试样的整体吸附件，使其浸渍于试样中，11. A sample adsorption method, which is characterized in that, in a container containing a liquid or gas sample, an integral adsorbent for introducing the sample to the analysis device is accommodated, and it is immersed in the sample, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部，同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The structure of the monolithic adsorbent is as follows: the monolithic structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the monolithic structure, and at the same time, chemical substances are coated or chemically combined on the monolithic body to perform surface treatment. , 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 12.试样吸附方法，其特征在于，在收纳有液体或气体试样的容器内，收纳用于向分析装置导入试样的整体吸附件，搅拌试样和该整体吸附件，使其吸附试样中的对象成分，12. A sample adsorption method, characterized in that, in a container containing a liquid or gas sample, an integral adsorbent for introducing the sample into the analysis device is accommodated, and the sample and the integral adsorbent are stirred to allow the sample to adsorb the sample. The object components in the sample, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部，同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The structure of the monolithic adsorbent is as follows: the monolithic structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the monolithic structure, and at the same time, chemical substances are coated or chemically combined on the monolithic body to perform surface treatment. , 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 13.试样吸附方法，其特征在于，在收纳有气体试样的容器内，收纳用于向分析装置导入试样的整体吸附件，进行被动采样，13. A sample adsorption method, characterized in that, in a container containing a gas sample, an integral adsorption member for introducing a sample into an analysis device is housed, and passive sampling is performed, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部，同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The structure of the monolithic adsorbent is as follows: the monolithic structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the monolithic structure, and at the same time, chemical substances are coated or chemically combined on the monolithic body to perform surface treatment. , 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 14.试样吸附方法，其特征在于，将收纳有用于向分析装置导入试样的整体吸附件的管插入容器气相部，同时，从容器外部通过容器盖将He、N2等惰性气体吹入试样中，使试样中的目标成分向容器气相部移动，保持在所述整体吸附件上，14. A sample adsorption method, which is characterized in that a tube containing an integral adsorbent for introducing a sample to an analysis device is inserted into the gas phase part of the container, and at the same time, an inert gas such as He or N is blown into the container from the outside of the container through the container cover. In the sample, the target component in the sample is moved to the gas phase part of the container and held on the integral adsorption member, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部，同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The structure of the monolithic adsorbent is as follows: the monolithic structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the monolithic structure, and at the same time, chemical substances are coated or chemically combined on the monolithic body to perform surface treatment. , 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 15.试样吸附装置，其特征在于，在液体或气体试样的收纳容器或通道上，设有具有整体结构体的过滤器和用于向分析装置导入试样的整体吸附件，15. The sample adsorption device is characterized in that, on the storage container or channel of the liquid or gas sample, a filter with an integral structure and an integral adsorbent for introducing the sample to the analysis device are provided, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部、同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The structure of the monolithic adsorbent is as follows: the monolithic structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the monolithic structure, and at the same time, chemical substances are applied or chemically bonded to the monolithic body to perform surface treatment. , 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 16.如权利要求15所述的试样吸附装置，其特征在于，将所述过滤器形成为容器形，将用于吸附目标成分的所述用于向分析装置导入试样的整体吸附件设置在其内部。16. The sample adsorption device according to claim 15, wherein the filter is formed in a container shape, and the integral adsorption member for introducing the sample into the analysis device for adsorbing the target component is provided. inside it. 17.如权利要求15所述的试样吸附装置，其特征在于，使形成的所述过滤器中的所述用于向分析装置导入试样的整体结构体的通孔大于所述整体吸附件的通孔。17. The sample adsorption device according to claim 15, wherein the through hole of the integral structure for introducing the sample into the analysis device in the formed filter is larger than the integral adsorption member. through holes. 18.如权利要求15所述的试样吸附装置，其特征在于，使所述过滤器中的所述整体结构体通过亲水性或疏水性化合物或者离子性官能团进行反应。18. The sample adsorption device according to claim 15, wherein the monolithic structure in the filter is reacted with a hydrophilic or hydrophobic compound or an ionic functional group. 19.试样吸附装置，其特征在于，将用于向分析装置导入试样的整体吸附件配置在旋转搅拌器上，通过该搅拌器的旋转使目标成分吸附在该用于向分析装置导入试样的整体吸附件上，19. A sample adsorption device, characterized in that an integral adsorption member for introducing a sample into an analysis device is arranged on a rotary stirrer, and the target component is adsorbed on the sample for introduction into an analysis device by the rotation of the stirrer. On a monolithic adsorbent like this, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面，同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The composition of the integral adsorbent is as follows: the integral structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the integral structure, and at the same time, chemical substances are coated or chemically combined on the integral structure to perform surface treatment, 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials. 20.试样吸附装置，其特征在于，在液体或气体试样中的目标成分的吸附或萃取中，将用于向分析装置导入试样的整体吸附件安装在可密合的容器内，由此可提高试样接触效率，20. The sample adsorption device is characterized in that, in the adsorption or extraction of the target component in the liquid or gas sample, the integral adsorbent for introducing the sample to the analysis device is installed in a sealable container, by This improves sample contact efficiency, 所述整体吸附件的构成为：使整体结构体含有吸附材料，且使该吸附材料暴露在该整体结构体表面部，同时在该整体结构体上将化学物质涂布或化学结合而进行表面处理，The structure of the monolithic adsorbent is as follows: the monolithic structure contains an adsorbent material, and the adsorbent material is exposed on the surface of the monolithic structure, and at the same time, chemical substances are coated or chemically combined on the monolithic body to perform surface treatment. , 所述吸附材料是选自活性炭、石墨碳、碳纳米管、富勒烯、分子筛、沸石、硅藻土、二乙烯基苯共聚物、碳分子筛、活性氧化铝、弗罗里硅土中的一种或多种的混合的材料。The adsorption material is selected from activated carbon, graphite carbon, carbon nanotubes, fullerenes, molecular sieves, zeolites, diatomaceous earth, divinylbenzene copolymers, carbon molecular sieves, activated alumina, florisil. A mixture of one or more materials.
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